CA2266586A1 - Process for incorporating an active substance in a moulded plastic part - Google Patents
Process for incorporating an active substance in a moulded plastic part Download PDFInfo
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- CA2266586A1 CA2266586A1 CA002266586A CA2266586A CA2266586A1 CA 2266586 A1 CA2266586 A1 CA 2266586A1 CA 002266586 A CA002266586 A CA 002266586A CA 2266586 A CA2266586 A CA 2266586A CA 2266586 A1 CA2266586 A1 CA 2266586A1
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- dendrimer
- plastic
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- fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/003—Dendrimers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/005—Dendritic macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/02—Polyamines
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/79—Polyolefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/12—Applications used for fibers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
Abstract
Process for incorporating an active substance in an object partly or entirely consisting of a plastic, by bringing the object into contact with an active substance, the plastic of the object contains a dendrimer with terminal groups that are compatible with the plastic. The process is for example suitable for dying fibres.
Description
CA 02266~86 1999-03-l9 PROCESS FOR INCORPORATING AN ACTIVE
SUBSTANCE IN A MOULDED PLASTIC PART
s The invention relates to a process for incorporating an active substance in an object partly or entirely ~isting of ~ plastic, by bringing the object into contact with the active substance.
Such a process is known from Kirk Othmer, Encyclopedia of Chemical Technology, Vol. 8 (1993), pp.
672-753. Described herein is the dying of plastic fibres in a bath containing a solution of a dye, in '- 15 which the dye, in this case the active substance, penetrates the fibre.
A drawback of the known process is that the active substance is with difficulty absorbed into the plastic. It is for example not really possible to dye polypropylene fibres because the dye does not, or only with great difficulty, penetrat~the polypropylene fibre.
The aim of the invention is to provide a process that does not possess the aforementioned drawback.
Surprisingly, it has now been found that the - active substance is very well absorbed if the plastic of the object contains a dendrimer with terminal groups that are compatible with the plastic.
A further advantage is that new combinations of active substances and~ ,..cr~Jhave become possible, because active substances that are not kr Aot tt all/
absorbed into the plastic itself are absorbed into the plastic¦co...p~ containing the dendrimer.
The invention creates new, surprising possibilities. It is for example possible for a highly effective active substance that cannot endure the r ~~
CA 02266~86 1999-03-19 WO98/12376 PCT~L97/00527 processing of the plastic into the object - for example because the active substance degrades at the temperatures prevailing during the processing - to be incorporated in the plastic after the processing.
In the context of the invention 'dendrimers' are understood to be three-dimensional, highly branched oligomeric or polymeric molecules. The dendrimers according to the invention may contain a nucleus, a number of generations of branches and terminal groups.
A generation of branches consists of structural units ABx, in which x > or = 2, which are radially bound to the nucleus or to the structural units of the previous generation and extend outwards. A subsequent generation may form because for example groups A react with groups B of the previous generation.
The structural units may either be the same with each subsequent generation (repeat themselves) or they may differ. Dendrimers can be characterised by a degree of branching. The 'degree of branching' of a dendrimer of a particular generation is here understood to be the ratio of the number of branches present and the maximum possible number of branches in a completely branched dendrimer of the same generation.
The branches may occur with varying degrees of regularity. The branches at the outside surface of the dendrimers used in the context of the invention may for example all be of the same generation, but they may also be of different generations. The latter may for example be the case if the synthesis of the dendrimers proceeds in a less controlled manner.
'Dendrimers' are according to the invention understood to be completely branched dendrimers, dendrimers with defects in their branched structure, dendrimers with an incomplete degree of branching, asymmetrically branched dendrimers, star polymers, highly branched polymers, highly branched copolymers CA 02266~86 1999-03-19 and/or block copolymers of highly branched and non-highly branched polymers. Preferably the degree of branching is at least 50~, even more preferably at least 75~.
Preferably use is made of completely branched dendrimers, dendrimers with defects in their branched structure, dendrimers with an incomplete degree of branching, or asymmetrically branched dendrimers.
Because of the dendrimer's three-dimensional structure, there are cavities between the branches. The shape and the dimensions of these cavities vary in accordance with the generation, the chemical composition of the structural units and the degree of branching. It is possible to influence the degree of branching and the shape and dimensions of the cavities between the branches during the preparation of the dendrimer. This can be achieved among other ways by varying for example the chemical composition~ ~ the structural units' molecular weight, by increasing or decreasing the degree of branching or by disturbing the regularity in the branches' composition.
It is possible to influence the degree in which and rate at which the active substance is absorbed into the moulded part by varying the cavities' 2S shape and dimensions The dendrimers' terminal groups consist of the non-reacted groups B of the structural units ABx.
The-terminal groups B may themselves be compatible with the plastic of the moulded part that is brought into contact with the active substance. If the terminal groups B are themselves not, ~r insufficiently, B
~ L~ ~; n ~ 1 9r~
compatible with the plastic, ~ ~ can ~e modified with the aid of a modifying compound to yield modified terminal groups that are compatible with the plastic.
The fact that the terminal groups are compatible with the plastic means that the dendrimer CA 02266~86 1999-03-19 WO 98/12376 PCT/NLg7/00527 can be well dispersed in the plastic.
If the plastic of the moulded part is non-polar, a compound that is also non-polar is used as the modifying compound. If the plastic is polar, a compound that is also polar is used.
The type of modifying compound to be used will to a great extent depend on the modifying compound's reactivity with respect to the dendrimer's terminal group B. Preferably a compound is chosen that reacts as completely as possible with the dendrimer's terminal group.
Modifying compounds suitable for appending non-polar groups to the dendrimer's terminal groups are for example aliphatic halogenides, aliphatic alcohols, phenols, aliphatic and aromatic carboxylic acids, fatty acids, esters of aliphatic carboxylic acids and aromatic or aliphatic alcohols, esters of aromatic carboxylic acids and aromatic or aliphatic alcohols, aliphatic or aromatic epoxides, aliphatic or aromatic isocyanates, aliphatic or aromatic amides, aliphatic or aromatic amines, completely or incompletely fluorinated aliphatic compounds, sulphonic acids and derivatives of sulphonic acids, compounds containing phosphorus or compounds containing silicon. Mixtures of such compounds are also suitable. Preferably a compound that modifies the terminal group with an alkyl group is used as a non-polar compound, because this generally results in a very good compatibility with non-polar plastics, such as polyolefines. Examples of modifying compounds that modify the terminal groups with an alkyl group are fatty acids, alcohols derived from a fatty acid, amines derived from a fatty acid, isocyanates corresponding to a fatty acid, epoxides corresponding to a fatty acid and halogenides corresponding to a fatty acid. Examples are stearyl alcohol, dodecyl phenol, 4,4,5,5,5-pentafluoro-n-pentanol-1, stearamide, palmityl CA 02266~86 1999-03-19 WO98/12376 PCT~97/00527 isocyanate, palmitoyl chloride, stearyl chloride, pentafluoropropionyl chloride, lauric acid, myristic acid, palmitic acid, stearic acid, perfluorononanoic acid and the mixture of alkane carboxylic acids known as "Montanwachs". More preferably use is made of a saturated or (mono- or poly)unsaturated fatty acid.
Preferably use is made of a modifying compound that modifies the terminal group with an alkyl group having 6-50 C atoms, more preferably with an alkyl group having 12-30 atoms, even more preferably with an alkyl group having 16-20 atoms.
Other compounds suitable for modifying the terminal groups with non-polar groups are oligomer and/or polymer chains that are compatible with the plastic matrix into which the dendrimer must be mixed.
Compounds suitable for modifying the dendrimer's terminal groups with polar groups are for example polyacrylates, polymethacrylates, polyvinyl alcohols, polyvinyl esters, polyvinyl ethers, polyurethanes, polyurea, polyisocyanates, polyvinyl pyridines, polyvinyl pyrrolidones, polyethylene glycols, polyethylene imines, polycarbonates, polycaprolactones, nylons, styrene-acrylonitrile copolymers (SAN), styrene-maleic anhydride copolymers (SMA), polyphenylene oxides (PPO), Jeff amines, telechelic polyesters, copolymers of alkenes with carbon monoxide, copolymers of styrene, polymers of acrylic acid and polymers of methacrylic acid.
Preferably use is made of dendrimers of which at least 30% of the terminal groups has reacted with a modifying compound, more preferably 40-75% of the terminal groups has reacted with a modifying compound.
This ensures that the dendrimer is well miscible in the plastic of the object and that the active substance is rapidly absorbed.
Regularly composed dendrimers can be prepared CA 02266~86 1999-03-19 WO9U12376 PCT~L97t~527 via a divergent process, according to which successive generations of dendrimer molecules are generated in repeated reaction sequences starting from a multifunctional nucleus, the branches being generateB
in a systematic manner. Such a process is for example described in EP-A-575 596. It is also possible to first synthesize regularly branched segments via a convergent process and to couple them to a multifunctional nucleus in a last step. It is furthermore possible to use combinations of convergent and divergent processes.
Less regularly composed dendrimers can for example be prepared via polycondensation, ring-opening polymerisation or addition polymerisation.
Highly branched polymers can be prepared for example via radical or anionic or cationic chain polymerisation of monomers of type AB, where A is a vinyl group and B a group that is activated via an initiation commonly used for chain polymerisation. Such a polymerisation is for example described in J.M.J.
Frechet, Science 269 (1995), pp. 1080-1083.
It is also possible to prepare a highly branched polymer through cationic polymerisation of ethylene imine. The resultant highly branched polymer has many reactive functional terminal groups.
Dendrimers that are suitable in the context of the invention are dendrimers based on for example a polyester, polyether, polythioether, polyamide, polyether ketone, polyalkylene imine, polyamidoamine, polyether amide, polyarylene, polyalkane, polyalkylene aromatic compounds, polyarylacetylene and/or a dendrimer containing phosphorus or silicon, or a combination thereof. Preferably use is made of a dendrimer based on polyalkylene imine or polyamidoamine. It is also possible to use a highly branched polyester.
When use is made of the dendrimers according CA 02266~X6 1999-03-19 to the invention with which generations of branches are demonstrable, use is preferably made of dendrimers of the 2nd up to and including the 5th, more preferably the 3rd or the 4th, generation.
Active substances that can be used in the process according to the invention are for example antistatic agents, adhesives, odorous substances, fireproofing agents, flame retardants, antioxidants, UV-stabilisers and dyes. Preferably use is made of dyes.
To speed up the incorporation of the active ~ substance a low molecular compound that swells the plastic can be used.
Examples of suitable types of dyes are azo, azine, perinone, anthraquinone, xanthene, phthalocyanine, triarylmethane, indophenol, coumarin ~ 'J~
and diazomethane~ig~rtq. Mixtures of dyes are also suitable. Criteria in the selection of the dye are for example the desired colour and the pigment's thermal and UV resistance.
By using the process according to the invention the active substances can be incorporated in objects of many kinds of plastics. Thermoplastics, thermosetting plastics as well as rubbers are suitable.
The invention is suitable for both homo- and copolymers. Mixtures of plastics can also be used.
Examples of suitable plastics are polyolefines, such as low-density polyethylene (LDPE), high-density polyethylene (HDPE), vLDPE, LLDPE, polypropylene (PP), which is understood to include PP homopolymers and PP
copolymers such as random ethylene/propylene copolymers and PP block copolymers with an ethylene/propylene phase, vinyl polymers, styrene polymers, acrylic polymers, fluorine-containing polymers, polyamides, polycarbonates, polyoxyalkylenes, polyimides, polybenzimidazoles, polyphenylene oxides, , CA 02266~86 1999-03-19 polyacrylonitriles, polyesters, phenol-formaldehydes, aminoplastics, epoxy resins, polyurethanes, styrene-butadiene rubber, butyl rubber, chlorobutyl rubber, chloroprene rubber, nitrile rubber, butadiene rubber, isoprene rubber, ethylene-propylene rubbers (EPM, ethylene-propylene monomer, and EPDM, ethylene-propylene-diene monomer), silicone rubbers, urethane rubbers, acrylate rubbers, fluorine-containing rubbers and/or cyclopentene rubbers.
In the process according to the invention the - object can in several ways be brought into contact with ~ the active substance. It is for example possible to immerse the object or coat it with a liquid active substance or to treat the object in this manner with a solution, a melt, a slurry or an emulsion of an active substance. It is also conceivable that an object is brought into contact with a gaseous active substance or with an active substance in the solid phase.
In a preferred embodiment the invention relates to a process in which a polyole~ine, more preferably polypropylene, is used as the plastic of the object. By preference the plastic of these objects comprises polypropylene imine dendrimers. By preference the dendrimer contains ~ polair fatty acid end groups.
Such object can very well be printed with the aid of the process according to the invention, without having to subject the surface of the object to a spe-cial treatment, such as a corona treatment. Such objects can also very well be dyed, by immersing them in a bath containing a solution of a dye. In this way objects o~ a polyole~ine with very deep, intense colours can be obtained, whereas this is not achievable, or achievable with great difficulty, with the known processes.
The advantages o~ the invention become particularly evident if the process according to the CA 02266~86 1999-03-19 invention is used in dying fibres, in particular polypropylene fibres.
In particular, dying fibres, especially polypropylene fibres, according to the known processes involves problems, in connection with the poor absorption of the dye into the fibres. It is not possible to modify the fibres' surface to improve the absorption of dye, such as etching the fibre surface, because these modifications of the fibres generally adversely affect the fibres' mechanical properties, such as tensile strength and stiffness.
~- Fibres that have been dyed with the aid of the process according to the invention can have bright, deep colours and there are no problems with the fibres' mechanical properties.
By preference for dying the fibers a polar dye that cannot dissolve in water is used. Examples of such dyes are the disperse dyes. In this way ~ fibers have a ~ high washing resistance,d~ obt~;~
The invention will be elucidated with reference to the examples, without being restricted thereto.
In the following examples use is made of polypropylene imine dendrimers. The preparation of such 25 dendrimers is described in EP-A-575 596 and EP-A-707 611. Amine-terminated polypropylene imine dendrimers according to the aforementioned applications have 16 amine terminal groups in the third generation and 32 amine terminal groups in the fourth generation.
ExamPle I
4.84 grams of an amine-terminated polypropylene imine dendrimer of the fourth generation (corresponding to 44.0 milliequivalents of NH2), 12.50 grams of stearic acid (corresponding to 43.9 milliequivalents) and 20 ml of xylene were stirred and CA 02266~86 1999-03-19 WO98/12376 PCT~97/~527 heated to 180~C for half an hour in a triple-neck flask with a volume of 250 ml. The triple-neck flask was fitted with a Dean-Stark set-up with a reflux cooler.
Next, the xylene solution was poured into 250 ml of methanol while it was still hot, which resulted in the formation of a precipitate. The precipitate was removed through filtration, washed with methanol and dried in a vacuum at 45~C. The yield was 12.8 grams of a yellowish white powder. Infrared and nuclear spin resonance spectra showed that all the amine groups of the dendrimer had been converted into amide by the stearic acid. The dendrimer modified with stearic acid had a melting point of 82-83~C.
In a mini-extrusion apparatus a mixture of 4.5 g of an isotactic polypropylene with a melt index of 20 g/10 min. (230~C, 2.16 kg) and the dendrimer was successively extruded in amounts of 1, 2 and 4 percent by weight. A thread was obtained via the extruder's drain opening, which was stretched via a rapidly rotating winding machine to obtain fibres with a thickness of about 70 micrometres.
Exam~le II
4.24 grams of an amine-terminated polypropylene imine dendrimer of the fourth generation (corresponding to 38.6 milliequivalents of NH2) and 5.48 grams of stearic acid (corresponding to 19.3 milliequivalents, that is, half of the number of amine groups used) were heated to 150~C for 1 hour, at a reduced pressure of 20 mm of mercury, in a 250-ml two-neck flask fitted with a distillation set-up with a cooler. After cooling a yellow-white solid substance had formed, which, as demonstrated by spectroscopic examination, no longer contained any free stearic acid and had a melting point of 74-76~C.
Polypropylene fibres were prepared as CA 02266~86 1999-03-19 WO98/12376 PCT~97/~527 described in Example I.
ExamPle III
10.56 grams an amine-terminated polypropylene imine dendrimer of the third generation (corresponding to 100.2 milliequivalents of NH2) and 28.44 grams of stearic acid (corresponding to 100.0 milliequivalents) were heated to 150~C for 1 hour, at a reduced pressure of 20 mm of mercury, in a 250-ml two-neck flask fitted with a distillation set-up with a cooler. After cooling a yellow-white solid substance had formed, which no longer contained any free stearic acid. The product had a melting point of 81-82~C.
Polypropylene fibres were prepared as described in Example I.
ExamPle IV
14.19 grams of an amine-terminated polypropylene imine dendrimer of the third generation (corresponding to 134.6 milliequivalents of NH2) and 19.11 grams of stearic acid (corresponding to 67.2 milliequivalents, that is, half of the number of amine groups used) were heated to 150~C for 1 hour, at a reduced pressure of 20 mm of mercury, in a 250-ml two-neck flask fitted with a distillation set-up with a cooler. After cooling a yellow-white solid substance had formed, which no longer contained any free stearic acid.
Polypropylene fibres were prepared as described in Example I.
Comparative Ex~eriment A
Polypropylene fibre without an added modified dendrimer was obtained through extrusion at 220OC of the polypropylene used in Example I, otherwise as described in Example I.
CA 02266~86 1999-03-19 ExamPle V
An acid dye bath containing the dye Tectilon Blue GC-G (Acid Blue 344) was prepared by dissolving 1 gram of this dye in a solution of 2.8 ml of concentrated sulphuric acid in 1 litre of water, which had a pH of about 1.6. Bundles of polypropylene fibres with a length of about 50 mm, prepared according to Examples I-IV and Comparative Experiment A, were placed in 10 ml of the dye solution. While the solution was stirred via a magnetic stirrer, it was heated to 80~C
in a water bath in approx. 30 minutes and kept at this - temperature for two hours. Then the fibre bundle was removed from the dye solution and washed twice in running water of approx. 20~C for about ten seconds.
Next, the fibre bundle was~ dried to the air.
The amount of ~i~.cn~¦absorbed by the fibres was visually assessed. In this assessment the following desiqnations were assigned:
0 colourless, the same as the starting material 1 slight colouring 2 moderate colouring 3 deep colouring 4 very deep colouring The results of the colour assessments of the different fibres are shown in Table 1.
-. ~ . ,, ~, .
CA 02266~86 1999-03-19 WO98/12376 PCT~97/~527 Table l Assessment of the colour of fibres dyed with Tectilon Blue GC-G (Acid Blue 344) fibre l wt.% 2 wt.% 4 wt.%
according to Example I l 2 2 Example II 2 3 4 Fibre according to Comparative Experiment A: 0.
This shows that the results obtained with the fibres prepared from the compositions according to the invention are considerably better than those obtained with fibres made of polypropylene without the added modified dendrimer. The best results are obtained with fibres prepared from the composition according to Example II, in which 50 % of the terminal groups of the dendrimer is modified.
Exam~le VI
The process according to Example VI was repeated using the dye Tectilon Blue 4R-Ol (Ciba-Geigy). The assessment of the colour of the resulting fibres is given in Table 2.
CA 02266~86 1999-03-19 WO98/12376 PCT~97/OOS27 Table 2 Assessment of the colour of fibres dyed with Tectilon Blue 4R-Ol 5 fibres l wt.~ 2 wt.% 4 wt.%
according to Example I l 2 2 Example II l 3 4 Fibres according to Comparative Experiment A: 0.
Half of the deeply coloured fibre bundle containing 4 %
modified dendrimer according to Example II was placed in lO ml of water of 40~C for 2 hours, with stirring.
After drying the visual assessment of the colouring was unchanged.
ExamPle VII
The process according to Example V was repeated with the dye Tectilon Red 2B (Ciba-Geigy). The visual assessment of the colouring is given in Table 3.
Table 3 Assessment of the colour of fibres dyed with Tectilon Red 2B.
fibre l wt.% 2 wt.% 4 wt.%
according to Example I l 3 3 Example II 2 3 4 Fibre according to Comparative Experiment A: 0.
CA 02266586 l999-03-l9 ~ -- 15 --Half of the deeply coloured fibre bundle containing 4 %
additive according to Example II was placed in 10 ml of water of 40~C for 2 hours, with stirring. After drying the visual assessment of the colouring was unchanged.
Exam~le VIII
The process according to Example V was repeated with the dye Tectilon Yellow 2G 200 and Erionyl Blue RL. The colouring of the fibres containing 2 and 4 percent by weight dendrimer according to Examples 2 Up to and including 4 was very deep. A
moderate to deep colouring was obtained already with 1 ~ of the dendrimer.
No loss of colour occurred in treatment with water of 15 40~C as described in Example VIII of the deeply coloured fibres containing 4 % dendrimer according to Example II.
Exam~le IX
An acid dye bath containing the dye Erionyl Red 2B was obtained by dissolving 1 gram of this dye in 1 liter of a solution of acetic acid in water with a pH
of 3.1. Fibres were dyed in the manner described in Example VIII. The visual assessment of the colouring is 25 given in Table 4. No loss of colour occurred in treatment with water of 40~C as described in Example VI
of the deeply coloured fibres containing 4 % modified dendrimer according to Example II.
CA 02266~86 1999-03-19 WO98112376 PCT~L97/00527 Table 4 Assessment of the colour of fibres dyed with Erionyl Red 2B in diluted acetic acid 5 fibre l wt.% 2 wt.% 4 wt.%
according to Example I 2 3 3 Example II 2 3 4 Example III - 2 3 lO Example IV - 4 4 Fibre according to Comparative Experiment A: l.
Exam~le X
A disperse dye bath was prepared by dispersing l gram of the dye Terasil Blue 3RL-02 in l liter water. Polypropylene fibers prepared according to examples II en IV were dyed in this bath, according to the process as further described in example V.
The colouring of the fibers, comprising 2 wt.% of dendimer, was very deep.
The washing resistance was determined by treating a bundle of lO fibers with a 0.5 wt.% soap solution during 45 minutes at 50~ according to ISO 105.
There were no colour differences before and after the treatment of the fibers.
SUBSTANCE IN A MOULDED PLASTIC PART
s The invention relates to a process for incorporating an active substance in an object partly or entirely ~isting of ~ plastic, by bringing the object into contact with the active substance.
Such a process is known from Kirk Othmer, Encyclopedia of Chemical Technology, Vol. 8 (1993), pp.
672-753. Described herein is the dying of plastic fibres in a bath containing a solution of a dye, in '- 15 which the dye, in this case the active substance, penetrates the fibre.
A drawback of the known process is that the active substance is with difficulty absorbed into the plastic. It is for example not really possible to dye polypropylene fibres because the dye does not, or only with great difficulty, penetrat~the polypropylene fibre.
The aim of the invention is to provide a process that does not possess the aforementioned drawback.
Surprisingly, it has now been found that the - active substance is very well absorbed if the plastic of the object contains a dendrimer with terminal groups that are compatible with the plastic.
A further advantage is that new combinations of active substances and~ ,..cr~Jhave become possible, because active substances that are not kr Aot tt all/
absorbed into the plastic itself are absorbed into the plastic¦co...p~ containing the dendrimer.
The invention creates new, surprising possibilities. It is for example possible for a highly effective active substance that cannot endure the r ~~
CA 02266~86 1999-03-19 WO98/12376 PCT~L97/00527 processing of the plastic into the object - for example because the active substance degrades at the temperatures prevailing during the processing - to be incorporated in the plastic after the processing.
In the context of the invention 'dendrimers' are understood to be three-dimensional, highly branched oligomeric or polymeric molecules. The dendrimers according to the invention may contain a nucleus, a number of generations of branches and terminal groups.
A generation of branches consists of structural units ABx, in which x > or = 2, which are radially bound to the nucleus or to the structural units of the previous generation and extend outwards. A subsequent generation may form because for example groups A react with groups B of the previous generation.
The structural units may either be the same with each subsequent generation (repeat themselves) or they may differ. Dendrimers can be characterised by a degree of branching. The 'degree of branching' of a dendrimer of a particular generation is here understood to be the ratio of the number of branches present and the maximum possible number of branches in a completely branched dendrimer of the same generation.
The branches may occur with varying degrees of regularity. The branches at the outside surface of the dendrimers used in the context of the invention may for example all be of the same generation, but they may also be of different generations. The latter may for example be the case if the synthesis of the dendrimers proceeds in a less controlled manner.
'Dendrimers' are according to the invention understood to be completely branched dendrimers, dendrimers with defects in their branched structure, dendrimers with an incomplete degree of branching, asymmetrically branched dendrimers, star polymers, highly branched polymers, highly branched copolymers CA 02266~86 1999-03-19 and/or block copolymers of highly branched and non-highly branched polymers. Preferably the degree of branching is at least 50~, even more preferably at least 75~.
Preferably use is made of completely branched dendrimers, dendrimers with defects in their branched structure, dendrimers with an incomplete degree of branching, or asymmetrically branched dendrimers.
Because of the dendrimer's three-dimensional structure, there are cavities between the branches. The shape and the dimensions of these cavities vary in accordance with the generation, the chemical composition of the structural units and the degree of branching. It is possible to influence the degree of branching and the shape and dimensions of the cavities between the branches during the preparation of the dendrimer. This can be achieved among other ways by varying for example the chemical composition~ ~ the structural units' molecular weight, by increasing or decreasing the degree of branching or by disturbing the regularity in the branches' composition.
It is possible to influence the degree in which and rate at which the active substance is absorbed into the moulded part by varying the cavities' 2S shape and dimensions The dendrimers' terminal groups consist of the non-reacted groups B of the structural units ABx.
The-terminal groups B may themselves be compatible with the plastic of the moulded part that is brought into contact with the active substance. If the terminal groups B are themselves not, ~r insufficiently, B
~ L~ ~; n ~ 1 9r~
compatible with the plastic, ~ ~ can ~e modified with the aid of a modifying compound to yield modified terminal groups that are compatible with the plastic.
The fact that the terminal groups are compatible with the plastic means that the dendrimer CA 02266~86 1999-03-19 WO 98/12376 PCT/NLg7/00527 can be well dispersed in the plastic.
If the plastic of the moulded part is non-polar, a compound that is also non-polar is used as the modifying compound. If the plastic is polar, a compound that is also polar is used.
The type of modifying compound to be used will to a great extent depend on the modifying compound's reactivity with respect to the dendrimer's terminal group B. Preferably a compound is chosen that reacts as completely as possible with the dendrimer's terminal group.
Modifying compounds suitable for appending non-polar groups to the dendrimer's terminal groups are for example aliphatic halogenides, aliphatic alcohols, phenols, aliphatic and aromatic carboxylic acids, fatty acids, esters of aliphatic carboxylic acids and aromatic or aliphatic alcohols, esters of aromatic carboxylic acids and aromatic or aliphatic alcohols, aliphatic or aromatic epoxides, aliphatic or aromatic isocyanates, aliphatic or aromatic amides, aliphatic or aromatic amines, completely or incompletely fluorinated aliphatic compounds, sulphonic acids and derivatives of sulphonic acids, compounds containing phosphorus or compounds containing silicon. Mixtures of such compounds are also suitable. Preferably a compound that modifies the terminal group with an alkyl group is used as a non-polar compound, because this generally results in a very good compatibility with non-polar plastics, such as polyolefines. Examples of modifying compounds that modify the terminal groups with an alkyl group are fatty acids, alcohols derived from a fatty acid, amines derived from a fatty acid, isocyanates corresponding to a fatty acid, epoxides corresponding to a fatty acid and halogenides corresponding to a fatty acid. Examples are stearyl alcohol, dodecyl phenol, 4,4,5,5,5-pentafluoro-n-pentanol-1, stearamide, palmityl CA 02266~86 1999-03-19 WO98/12376 PCT~97/00527 isocyanate, palmitoyl chloride, stearyl chloride, pentafluoropropionyl chloride, lauric acid, myristic acid, palmitic acid, stearic acid, perfluorononanoic acid and the mixture of alkane carboxylic acids known as "Montanwachs". More preferably use is made of a saturated or (mono- or poly)unsaturated fatty acid.
Preferably use is made of a modifying compound that modifies the terminal group with an alkyl group having 6-50 C atoms, more preferably with an alkyl group having 12-30 atoms, even more preferably with an alkyl group having 16-20 atoms.
Other compounds suitable for modifying the terminal groups with non-polar groups are oligomer and/or polymer chains that are compatible with the plastic matrix into which the dendrimer must be mixed.
Compounds suitable for modifying the dendrimer's terminal groups with polar groups are for example polyacrylates, polymethacrylates, polyvinyl alcohols, polyvinyl esters, polyvinyl ethers, polyurethanes, polyurea, polyisocyanates, polyvinyl pyridines, polyvinyl pyrrolidones, polyethylene glycols, polyethylene imines, polycarbonates, polycaprolactones, nylons, styrene-acrylonitrile copolymers (SAN), styrene-maleic anhydride copolymers (SMA), polyphenylene oxides (PPO), Jeff amines, telechelic polyesters, copolymers of alkenes with carbon monoxide, copolymers of styrene, polymers of acrylic acid and polymers of methacrylic acid.
Preferably use is made of dendrimers of which at least 30% of the terminal groups has reacted with a modifying compound, more preferably 40-75% of the terminal groups has reacted with a modifying compound.
This ensures that the dendrimer is well miscible in the plastic of the object and that the active substance is rapidly absorbed.
Regularly composed dendrimers can be prepared CA 02266~86 1999-03-19 WO9U12376 PCT~L97t~527 via a divergent process, according to which successive generations of dendrimer molecules are generated in repeated reaction sequences starting from a multifunctional nucleus, the branches being generateB
in a systematic manner. Such a process is for example described in EP-A-575 596. It is also possible to first synthesize regularly branched segments via a convergent process and to couple them to a multifunctional nucleus in a last step. It is furthermore possible to use combinations of convergent and divergent processes.
Less regularly composed dendrimers can for example be prepared via polycondensation, ring-opening polymerisation or addition polymerisation.
Highly branched polymers can be prepared for example via radical or anionic or cationic chain polymerisation of monomers of type AB, where A is a vinyl group and B a group that is activated via an initiation commonly used for chain polymerisation. Such a polymerisation is for example described in J.M.J.
Frechet, Science 269 (1995), pp. 1080-1083.
It is also possible to prepare a highly branched polymer through cationic polymerisation of ethylene imine. The resultant highly branched polymer has many reactive functional terminal groups.
Dendrimers that are suitable in the context of the invention are dendrimers based on for example a polyester, polyether, polythioether, polyamide, polyether ketone, polyalkylene imine, polyamidoamine, polyether amide, polyarylene, polyalkane, polyalkylene aromatic compounds, polyarylacetylene and/or a dendrimer containing phosphorus or silicon, or a combination thereof. Preferably use is made of a dendrimer based on polyalkylene imine or polyamidoamine. It is also possible to use a highly branched polyester.
When use is made of the dendrimers according CA 02266~X6 1999-03-19 to the invention with which generations of branches are demonstrable, use is preferably made of dendrimers of the 2nd up to and including the 5th, more preferably the 3rd or the 4th, generation.
Active substances that can be used in the process according to the invention are for example antistatic agents, adhesives, odorous substances, fireproofing agents, flame retardants, antioxidants, UV-stabilisers and dyes. Preferably use is made of dyes.
To speed up the incorporation of the active ~ substance a low molecular compound that swells the plastic can be used.
Examples of suitable types of dyes are azo, azine, perinone, anthraquinone, xanthene, phthalocyanine, triarylmethane, indophenol, coumarin ~ 'J~
and diazomethane~ig~rtq. Mixtures of dyes are also suitable. Criteria in the selection of the dye are for example the desired colour and the pigment's thermal and UV resistance.
By using the process according to the invention the active substances can be incorporated in objects of many kinds of plastics. Thermoplastics, thermosetting plastics as well as rubbers are suitable.
The invention is suitable for both homo- and copolymers. Mixtures of plastics can also be used.
Examples of suitable plastics are polyolefines, such as low-density polyethylene (LDPE), high-density polyethylene (HDPE), vLDPE, LLDPE, polypropylene (PP), which is understood to include PP homopolymers and PP
copolymers such as random ethylene/propylene copolymers and PP block copolymers with an ethylene/propylene phase, vinyl polymers, styrene polymers, acrylic polymers, fluorine-containing polymers, polyamides, polycarbonates, polyoxyalkylenes, polyimides, polybenzimidazoles, polyphenylene oxides, , CA 02266~86 1999-03-19 polyacrylonitriles, polyesters, phenol-formaldehydes, aminoplastics, epoxy resins, polyurethanes, styrene-butadiene rubber, butyl rubber, chlorobutyl rubber, chloroprene rubber, nitrile rubber, butadiene rubber, isoprene rubber, ethylene-propylene rubbers (EPM, ethylene-propylene monomer, and EPDM, ethylene-propylene-diene monomer), silicone rubbers, urethane rubbers, acrylate rubbers, fluorine-containing rubbers and/or cyclopentene rubbers.
In the process according to the invention the - object can in several ways be brought into contact with ~ the active substance. It is for example possible to immerse the object or coat it with a liquid active substance or to treat the object in this manner with a solution, a melt, a slurry or an emulsion of an active substance. It is also conceivable that an object is brought into contact with a gaseous active substance or with an active substance in the solid phase.
In a preferred embodiment the invention relates to a process in which a polyole~ine, more preferably polypropylene, is used as the plastic of the object. By preference the plastic of these objects comprises polypropylene imine dendrimers. By preference the dendrimer contains ~ polair fatty acid end groups.
Such object can very well be printed with the aid of the process according to the invention, without having to subject the surface of the object to a spe-cial treatment, such as a corona treatment. Such objects can also very well be dyed, by immersing them in a bath containing a solution of a dye. In this way objects o~ a polyole~ine with very deep, intense colours can be obtained, whereas this is not achievable, or achievable with great difficulty, with the known processes.
The advantages o~ the invention become particularly evident if the process according to the CA 02266~86 1999-03-19 invention is used in dying fibres, in particular polypropylene fibres.
In particular, dying fibres, especially polypropylene fibres, according to the known processes involves problems, in connection with the poor absorption of the dye into the fibres. It is not possible to modify the fibres' surface to improve the absorption of dye, such as etching the fibre surface, because these modifications of the fibres generally adversely affect the fibres' mechanical properties, such as tensile strength and stiffness.
~- Fibres that have been dyed with the aid of the process according to the invention can have bright, deep colours and there are no problems with the fibres' mechanical properties.
By preference for dying the fibers a polar dye that cannot dissolve in water is used. Examples of such dyes are the disperse dyes. In this way ~ fibers have a ~ high washing resistance,d~ obt~;~
The invention will be elucidated with reference to the examples, without being restricted thereto.
In the following examples use is made of polypropylene imine dendrimers. The preparation of such 25 dendrimers is described in EP-A-575 596 and EP-A-707 611. Amine-terminated polypropylene imine dendrimers according to the aforementioned applications have 16 amine terminal groups in the third generation and 32 amine terminal groups in the fourth generation.
ExamPle I
4.84 grams of an amine-terminated polypropylene imine dendrimer of the fourth generation (corresponding to 44.0 milliequivalents of NH2), 12.50 grams of stearic acid (corresponding to 43.9 milliequivalents) and 20 ml of xylene were stirred and CA 02266~86 1999-03-19 WO98/12376 PCT~97/~527 heated to 180~C for half an hour in a triple-neck flask with a volume of 250 ml. The triple-neck flask was fitted with a Dean-Stark set-up with a reflux cooler.
Next, the xylene solution was poured into 250 ml of methanol while it was still hot, which resulted in the formation of a precipitate. The precipitate was removed through filtration, washed with methanol and dried in a vacuum at 45~C. The yield was 12.8 grams of a yellowish white powder. Infrared and nuclear spin resonance spectra showed that all the amine groups of the dendrimer had been converted into amide by the stearic acid. The dendrimer modified with stearic acid had a melting point of 82-83~C.
In a mini-extrusion apparatus a mixture of 4.5 g of an isotactic polypropylene with a melt index of 20 g/10 min. (230~C, 2.16 kg) and the dendrimer was successively extruded in amounts of 1, 2 and 4 percent by weight. A thread was obtained via the extruder's drain opening, which was stretched via a rapidly rotating winding machine to obtain fibres with a thickness of about 70 micrometres.
Exam~le II
4.24 grams of an amine-terminated polypropylene imine dendrimer of the fourth generation (corresponding to 38.6 milliequivalents of NH2) and 5.48 grams of stearic acid (corresponding to 19.3 milliequivalents, that is, half of the number of amine groups used) were heated to 150~C for 1 hour, at a reduced pressure of 20 mm of mercury, in a 250-ml two-neck flask fitted with a distillation set-up with a cooler. After cooling a yellow-white solid substance had formed, which, as demonstrated by spectroscopic examination, no longer contained any free stearic acid and had a melting point of 74-76~C.
Polypropylene fibres were prepared as CA 02266~86 1999-03-19 WO98/12376 PCT~97/~527 described in Example I.
ExamPle III
10.56 grams an amine-terminated polypropylene imine dendrimer of the third generation (corresponding to 100.2 milliequivalents of NH2) and 28.44 grams of stearic acid (corresponding to 100.0 milliequivalents) were heated to 150~C for 1 hour, at a reduced pressure of 20 mm of mercury, in a 250-ml two-neck flask fitted with a distillation set-up with a cooler. After cooling a yellow-white solid substance had formed, which no longer contained any free stearic acid. The product had a melting point of 81-82~C.
Polypropylene fibres were prepared as described in Example I.
ExamPle IV
14.19 grams of an amine-terminated polypropylene imine dendrimer of the third generation (corresponding to 134.6 milliequivalents of NH2) and 19.11 grams of stearic acid (corresponding to 67.2 milliequivalents, that is, half of the number of amine groups used) were heated to 150~C for 1 hour, at a reduced pressure of 20 mm of mercury, in a 250-ml two-neck flask fitted with a distillation set-up with a cooler. After cooling a yellow-white solid substance had formed, which no longer contained any free stearic acid.
Polypropylene fibres were prepared as described in Example I.
Comparative Ex~eriment A
Polypropylene fibre without an added modified dendrimer was obtained through extrusion at 220OC of the polypropylene used in Example I, otherwise as described in Example I.
CA 02266~86 1999-03-19 ExamPle V
An acid dye bath containing the dye Tectilon Blue GC-G (Acid Blue 344) was prepared by dissolving 1 gram of this dye in a solution of 2.8 ml of concentrated sulphuric acid in 1 litre of water, which had a pH of about 1.6. Bundles of polypropylene fibres with a length of about 50 mm, prepared according to Examples I-IV and Comparative Experiment A, were placed in 10 ml of the dye solution. While the solution was stirred via a magnetic stirrer, it was heated to 80~C
in a water bath in approx. 30 minutes and kept at this - temperature for two hours. Then the fibre bundle was removed from the dye solution and washed twice in running water of approx. 20~C for about ten seconds.
Next, the fibre bundle was~ dried to the air.
The amount of ~i~.cn~¦absorbed by the fibres was visually assessed. In this assessment the following desiqnations were assigned:
0 colourless, the same as the starting material 1 slight colouring 2 moderate colouring 3 deep colouring 4 very deep colouring The results of the colour assessments of the different fibres are shown in Table 1.
-. ~ . ,, ~, .
CA 02266~86 1999-03-19 WO98/12376 PCT~97/~527 Table l Assessment of the colour of fibres dyed with Tectilon Blue GC-G (Acid Blue 344) fibre l wt.% 2 wt.% 4 wt.%
according to Example I l 2 2 Example II 2 3 4 Fibre according to Comparative Experiment A: 0.
This shows that the results obtained with the fibres prepared from the compositions according to the invention are considerably better than those obtained with fibres made of polypropylene without the added modified dendrimer. The best results are obtained with fibres prepared from the composition according to Example II, in which 50 % of the terminal groups of the dendrimer is modified.
Exam~le VI
The process according to Example VI was repeated using the dye Tectilon Blue 4R-Ol (Ciba-Geigy). The assessment of the colour of the resulting fibres is given in Table 2.
CA 02266~86 1999-03-19 WO98/12376 PCT~97/OOS27 Table 2 Assessment of the colour of fibres dyed with Tectilon Blue 4R-Ol 5 fibres l wt.~ 2 wt.% 4 wt.%
according to Example I l 2 2 Example II l 3 4 Fibres according to Comparative Experiment A: 0.
Half of the deeply coloured fibre bundle containing 4 %
modified dendrimer according to Example II was placed in lO ml of water of 40~C for 2 hours, with stirring.
After drying the visual assessment of the colouring was unchanged.
ExamPle VII
The process according to Example V was repeated with the dye Tectilon Red 2B (Ciba-Geigy). The visual assessment of the colouring is given in Table 3.
Table 3 Assessment of the colour of fibres dyed with Tectilon Red 2B.
fibre l wt.% 2 wt.% 4 wt.%
according to Example I l 3 3 Example II 2 3 4 Fibre according to Comparative Experiment A: 0.
CA 02266586 l999-03-l9 ~ -- 15 --Half of the deeply coloured fibre bundle containing 4 %
additive according to Example II was placed in 10 ml of water of 40~C for 2 hours, with stirring. After drying the visual assessment of the colouring was unchanged.
Exam~le VIII
The process according to Example V was repeated with the dye Tectilon Yellow 2G 200 and Erionyl Blue RL. The colouring of the fibres containing 2 and 4 percent by weight dendrimer according to Examples 2 Up to and including 4 was very deep. A
moderate to deep colouring was obtained already with 1 ~ of the dendrimer.
No loss of colour occurred in treatment with water of 15 40~C as described in Example VIII of the deeply coloured fibres containing 4 % dendrimer according to Example II.
Exam~le IX
An acid dye bath containing the dye Erionyl Red 2B was obtained by dissolving 1 gram of this dye in 1 liter of a solution of acetic acid in water with a pH
of 3.1. Fibres were dyed in the manner described in Example VIII. The visual assessment of the colouring is 25 given in Table 4. No loss of colour occurred in treatment with water of 40~C as described in Example VI
of the deeply coloured fibres containing 4 % modified dendrimer according to Example II.
CA 02266~86 1999-03-19 WO98112376 PCT~L97/00527 Table 4 Assessment of the colour of fibres dyed with Erionyl Red 2B in diluted acetic acid 5 fibre l wt.% 2 wt.% 4 wt.%
according to Example I 2 3 3 Example II 2 3 4 Example III - 2 3 lO Example IV - 4 4 Fibre according to Comparative Experiment A: l.
Exam~le X
A disperse dye bath was prepared by dispersing l gram of the dye Terasil Blue 3RL-02 in l liter water. Polypropylene fibers prepared according to examples II en IV were dyed in this bath, according to the process as further described in example V.
The colouring of the fibers, comprising 2 wt.% of dendimer, was very deep.
The washing resistance was determined by treating a bundle of lO fibers with a 0.5 wt.% soap solution during 45 minutes at 50~ according to ISO 105.
There were no colour differences before and after the treatment of the fibers.
Claims (13)
1. Process for incorporating an active substance in an object consisting partly or entirely of plastic, by bringing the object into contact with an active substance, characterised in that the plastic of the object contains a dendrimer with terminal groups that are compatible with the plastic.
2. Process according to Claim 1, characterised in that a completely branched dendrimer, a dendrimer with defects in the branched structure, a dendrimer with an incomplete degree of branching or an asymmetrically branched dendrimer is used as the dendrimer.
3. Process according to Claim 1 or Claim 2, characterised in that the dendrimer's terminal groups have been modified with a modifying compound to yield modified terminal groups that are compatible with the plastic.
4. Process according to Claim 3, characterised in that the modifying compound modifies the terminal groups with an alkyl group.
5. Process according to Claim 4, characterised in that the alkyl group contains 6-50 C atoms.
6. Process according to any one of Claims 3-5, characterised in that at least 30% of the terminal groups has reacted with the modifying compound.
7. Process according to any one of Claims 1-6, characterised in that a dendrimer of the 2nd up to and including the 5th generation is used.
8. Process according to any one of Claims 1-7, characterised in that polypropylene is used as the plastic of the object.
9. Process according to any one of Claims 1-8, characterised in that fibres are used as moulded parts.
10. Process according to claim 8 or 9, characterised in that, a polypropylene imine dendrimer is used in the plastic of the object.
11. Process according to claim 10, characterised in that, the dendrimer contains non-polar fatty acid end groups.
12. Moulded plastic part to be used in the process according to any one of Claims 3-8.
13. Plastic composition of the moulded plastic part to be used in the process according to any one of Claims 3-8.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL1004094 | 1996-09-23 | ||
| NL1004094A NL1004094C2 (en) | 1996-09-23 | 1996-09-23 | Method for incorporating an active substance into a plastic molded part. |
| PCT/NL1997/000527 WO1998012376A1 (en) | 1996-09-23 | 1997-09-22 | Process for incorporating an active substance in a moulded plastic part |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2266586A1 true CA2266586A1 (en) | 1998-03-26 |
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|---|---|---|---|
| CA002266586A Abandoned CA2266586A1 (en) | 1996-09-23 | 1997-09-22 | Process for incorporating an active substance in a moulded plastic part |
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| US (1) | US6232378B1 (en) |
| EP (1) | EP0927275B1 (en) |
| JP (1) | JP2001502015A (en) |
| CN (1) | CN1238018A (en) |
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| AU (1) | AU4225297A (en) |
| BR (1) | BR9711533A (en) |
| CA (1) | CA2266586A1 (en) |
| CZ (1) | CZ103199A3 (en) |
| DE (1) | DE69709663T2 (en) |
| EA (1) | EA199900323A1 (en) |
| HU (1) | HUP9903833A2 (en) |
| IL (1) | IL129087A0 (en) |
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| NO (1) | NO991379L (en) |
| PL (1) | PL332374A1 (en) |
| SK (1) | SK39099A3 (en) |
| TR (1) | TR199900643T2 (en) |
| WO (1) | WO1998012376A1 (en) |
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| FR2801594B1 (en) * | 1999-11-25 | 2003-08-15 | Hoechst Marion Roussel Inc | COLORED POLYPHENOXYDENDRIMERS, NOVEL SOLUBLE SUPPORTS, THEIR PREPARATION PROCESS AND THEIR USE IN ORGANIC SYNTHESIS |
| JP2003522266A (en) | 2000-02-09 | 2003-07-22 | チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド | Hyperbranched amphiphilic polymer additives and polymer compositions with increased surface energy |
| US6497959B1 (en) | 2000-03-30 | 2002-12-24 | General Electric Company | Use of dendrimers as a processing aid and surface modifier for thermoplastic resins |
| US20030135195A1 (en) * | 2002-01-16 | 2003-07-17 | Oscar Jimenez | Highly lubricious hydrophilic coating utilizing dendrimers |
| US7166657B2 (en) * | 2002-03-15 | 2007-01-23 | Eastman Kodak Company | Article utilizing highly branched polymers to splay layered materials |
| US6784267B1 (en) | 2002-07-25 | 2004-08-31 | Nalco Company | Polymers containing hyperbranched monomers |
| DE10318584A1 (en) * | 2003-04-24 | 2004-11-11 | Basf Ag | Highly branched polymeric stabilizers |
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| BE627902A (en) * | 1962-02-02 | |||
| US3361843A (en) * | 1964-06-15 | 1968-01-02 | Uniroyal Inc | Method of dyeing a blend of a polyolefin and a nitrogen containing polymer by using a dyebath containing lewis acids |
| US4631337A (en) * | 1983-01-07 | 1986-12-23 | The Dow Chemical Company | Hydrolytically-stable dense star polyamine |
| US5527524A (en) * | 1986-08-18 | 1996-06-18 | The Dow Chemical Company | Dense star polymer conjugates |
| US5530092A (en) | 1992-01-13 | 1996-06-25 | Dsm N.V. | Dendritic macromolecule and the preparation thereof |
| BE1007260A3 (en) * | 1993-07-08 | 1995-05-02 | Dsm Nv | Process for preparing a dendritic macromolecule OF. |
| BE1008134A3 (en) * | 1994-03-16 | 1996-01-23 | Dsm Nv | Preparation of star-branched polymers. |
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1996
- 1996-09-23 NL NL1004094A patent/NL1004094C2/en not_active IP Right Cessation
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1997
- 1997-09-22 CZ CZ991031A patent/CZ103199A3/en unknown
- 1997-09-22 JP JP10514540A patent/JP2001502015A/en active Pending
- 1997-09-22 TR TR1999/00643T patent/TR199900643T2/en unknown
- 1997-09-22 AT AT97940486T patent/ATE212083T1/en not_active IP Right Cessation
- 1997-09-22 PL PL97332374A patent/PL332374A1/en unknown
- 1997-09-22 IL IL12908797A patent/IL129087A0/en unknown
- 1997-09-22 WO PCT/NL1997/000527 patent/WO1998012376A1/en not_active Application Discontinuation
- 1997-09-22 BR BR9711533A patent/BR9711533A/en not_active Application Discontinuation
- 1997-09-22 HU HU9903833A patent/HUP9903833A2/en unknown
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- 1997-09-22 EP EP97940486A patent/EP0927275B1/en not_active Expired - Lifetime
- 1997-09-22 CN CN97199797A patent/CN1238018A/en active Pending
- 1997-09-22 EA EA199900323A patent/EA199900323A1/en unknown
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- 1997-09-22 CA CA002266586A patent/CA2266586A1/en not_active Abandoned
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| NL1004094C2 (en) | 1998-03-24 |
| DE69709663T2 (en) | 2002-10-17 |
| IL129087A0 (en) | 2000-02-17 |
| US6232378B1 (en) | 2001-05-15 |
| NO991379D0 (en) | 1999-03-22 |
| WO1998012376A1 (en) | 1998-03-26 |
| JP2001502015A (en) | 2001-02-13 |
| HUP9903833A2 (en) | 2000-04-28 |
| DE69709663D1 (en) | 2002-02-21 |
| CZ103199A3 (en) | 1999-09-15 |
| EP0927275B1 (en) | 2002-01-16 |
| EP0927275A1 (en) | 1999-07-07 |
| SK39099A3 (en) | 2000-03-13 |
| TR199900643T2 (en) | 1999-09-21 |
| PL332374A1 (en) | 1999-09-13 |
| ATE212083T1 (en) | 2002-02-15 |
| BR9711533A (en) | 1999-08-24 |
| AU4225297A (en) | 1998-04-14 |
| CN1238018A (en) | 1999-12-08 |
| EA199900323A1 (en) | 1999-12-29 |
| NO991379L (en) | 1999-05-21 |
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