CA2313256C - Catalyst system for the nco/oh reaction (polyurethane formation) - Google Patents
Catalyst system for the nco/oh reaction (polyurethane formation) Download PDFInfo
- Publication number
- CA2313256C CA2313256C CA002313256A CA2313256A CA2313256C CA 2313256 C CA2313256 C CA 2313256C CA 002313256 A CA002313256 A CA 002313256A CA 2313256 A CA2313256 A CA 2313256A CA 2313256 C CA2313256 C CA 2313256C
- Authority
- CA
- Canada
- Prior art keywords
- catalyst system
- compound
- general formula
- aryl
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
-
- 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
- C08G2110/00—Foam properties
- C08G2110/0008—Foam properties flexible
-
- 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
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
-
- 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
- C08G2290/00—Compositions for creating anti-fogging
Abstract
The present invention relates to a catalyst system for the production of polyurethane comprising catalysts for polyurethane formation and sterically hindered carbodiimides, which system is capable of lessening the "fogging" problem in the production of polyurethane materials, without impairing in particular the aging properties of the polyurethane materials thus produced.
Description
RC 206-Foreign Countries Bg/ngb/NT
CATALYST SYSTEM FOR THE NCO/OH REACTION (POLYURETHANE
FORMATION) FIELD OF THE INVENTION
The present invention relates to an improved catalyst system for the formation of polyurethane, by means of which the "fogging" problem in the production of polyurethane materials is successfully lessened, without impairing, in particular, the aging properties of the polyurethane materials thus produced.
BACKROUND OF THE INVENTION
It is known that the rate of polyurethane formation (NCO/OH reaction) is affected by the temperature of the raw materials and their structure, but is influenced predominantly by suitable catalysts. Compounds which have proven to be particularly suitable as catalysts for this previously described reaction are, in particular, tertiary amines, salts of weak acids (as basic catalysts) and organometallic compounds, such as organotin compounds (as electrophilic catalysts).
In the production of PU material, it is conventional for the catalysts used to remain in the finished material, provided that these catalysts are non-volatile or can be incorporated.
If volatile catalysts are used, even during the production of the material, they begin to volatilize as a result of the rise in temperature of the exothermic NCO/OH
reaction, a feature which is consistent with their low boiling point.
This leads to problems in maintaining industrial hygiene during the production of the PU materials and also to a continuous, slow release into the environment of the portions of volatile catalyst still remaining in the material ("fogging").
RC 206-Foreign Countries However, if, as described above, non-volatile catalysts, i.e. high-boiling catalysts, or catalysts which can be incorporated, are added, the PU materials produced with the aid of these catalysts exhibit poor aging properties due to the presence of these catalysts, because the catalysts in principle accelerate both the forward reaction, i.e.
the synthesis, and the backward reaction, i.e. the decomposition or the rearrangement of the PU materials. Physical test methods, such as the Ford test (in accordance with DIN 53 578) can be used as a measure of the decomposition or the impairment of the aging properties.
It is, therefore, usual to be dealing with PU materials which either create considerable problems in maintaining industrial hygiene during production or cause "fogging"
problems after their production or, in cases where non-volatile catalysts have been employed, exhibit poor aging properties, especially during long-term use.
Accordingly, the object is to provide PU catalyst systems which entail no problems in maintaining industrial hygiene and no "fogging" problems and, secondly, impart good aging properties to the finished PU material.
SUMMARY OF THE INVENTION
The present invention, therefore, provides a catalyst system comprising A) at least one catalyst for the NCO/OH reaction (polyurethane formation) and B) at least one sterically hindered carbodiimide, wherein component B) is present in a quantity of 1 wt.% up to 200 wt.%, based on the total quantity of component A).
CATALYST SYSTEM FOR THE NCO/OH REACTION (POLYURETHANE
FORMATION) FIELD OF THE INVENTION
The present invention relates to an improved catalyst system for the formation of polyurethane, by means of which the "fogging" problem in the production of polyurethane materials is successfully lessened, without impairing, in particular, the aging properties of the polyurethane materials thus produced.
BACKROUND OF THE INVENTION
It is known that the rate of polyurethane formation (NCO/OH reaction) is affected by the temperature of the raw materials and their structure, but is influenced predominantly by suitable catalysts. Compounds which have proven to be particularly suitable as catalysts for this previously described reaction are, in particular, tertiary amines, salts of weak acids (as basic catalysts) and organometallic compounds, such as organotin compounds (as electrophilic catalysts).
In the production of PU material, it is conventional for the catalysts used to remain in the finished material, provided that these catalysts are non-volatile or can be incorporated.
If volatile catalysts are used, even during the production of the material, they begin to volatilize as a result of the rise in temperature of the exothermic NCO/OH
reaction, a feature which is consistent with their low boiling point.
This leads to problems in maintaining industrial hygiene during the production of the PU materials and also to a continuous, slow release into the environment of the portions of volatile catalyst still remaining in the material ("fogging").
RC 206-Foreign Countries However, if, as described above, non-volatile catalysts, i.e. high-boiling catalysts, or catalysts which can be incorporated, are added, the PU materials produced with the aid of these catalysts exhibit poor aging properties due to the presence of these catalysts, because the catalysts in principle accelerate both the forward reaction, i.e.
the synthesis, and the backward reaction, i.e. the decomposition or the rearrangement of the PU materials. Physical test methods, such as the Ford test (in accordance with DIN 53 578) can be used as a measure of the decomposition or the impairment of the aging properties.
It is, therefore, usual to be dealing with PU materials which either create considerable problems in maintaining industrial hygiene during production or cause "fogging"
problems after their production or, in cases where non-volatile catalysts have been employed, exhibit poor aging properties, especially during long-term use.
Accordingly, the object is to provide PU catalyst systems which entail no problems in maintaining industrial hygiene and no "fogging" problems and, secondly, impart good aging properties to the finished PU material.
SUMMARY OF THE INVENTION
The present invention, therefore, provides a catalyst system comprising A) at least one catalyst for the NCO/OH reaction (polyurethane formation) and B) at least one sterically hindered carbodiimide, wherein component B) is present in a quantity of 1 wt.% up to 200 wt.%, based on the total quantity of component A).
DETAILED DESCRIPTION OF THE IINA'E1`T1U?", According to the present inventioil, particularly preferred catalyst systerns are those wherein the sterically hiiidered carbodimiides B) are present in the catalyst systeln in yuantities of 20 to 180 wt.%, more preferably 50 to 150 A,-t. /,, based on the total quantity of conzponent A).
All the known basic, as well as the electrophilic catalysts, which favor the formation of polyurethane al-e suitable as catalysts for the NCO/ON reaction. Such catalysts are described, for ey.ample, in Kunststoff-Handbuch, Volume 7, Polyurethane, Third newly revised Edition, Carl Hanser Verlag, Munich, Vierula, 1993, pp. 104 to 110.
Catalysts such as those described on page 105 of the above-mentioned publication are particularly suitable.
Such catalysts are, i.n particular (cyclo) aliphatic tertiary amines corresponding to the formulae (I) , R~Pv-?r [N-Rm] j N~R4 ~s . ) R ~a c~ N~ r,z wi;e, cin R denotes C, -C6 alkylene groups, R, to Rt are identical or diffei-ent and denote C1-C., alkyl, CS-C7 cycloalkyl, C(,-C,() aryl and C(,-C,(, arylmethyl or wherein groups Ri and R, and/or R~ and R4 can be bonded to one anotber via C,-C-, alkvlene ('roups c.ontaining 0 to 2 hetero atoms, such as nitro(,en, sulfur or ox~~~~eii, in the car-bon chain, n denotus inte,_,ers from 2 to 6, nl denotes lile nur7-ibers ? and ', and RC 206-Foreign Countries 1 denotes integers from 0 to 4.
Also to be mentioned are (cyclo)aliphatic aminoethers corresponding to formula (II) R6~N-R-O-R-N~R8 (II), R' Rg wherein R6 to Ry have the same meanings as groups Rl to R5 and R denotes C1-C6 alkylene groups.
Also to be mentioned are (cyclo)aliphatic amidines corresponding to formula (III) R10(-, N-C=N-R,a R" R' 2 (III), wherein Rlo to R13 have the same meanings as groups Rl to R5 or Rto and R13 and/or Rll and R12 can be bonded to one another via C2-C5 alkylene groups.
Also to be mentioned are bicyclic diamines corresponding to formula (IV) R
\N
R /
N\
R
(IV), wherein R has the same meaning as R in formula (II).
Also to be mentioned ai-e organotin compounds correspondinL, to fornnula (V) O
0 R,s Sn R1 \ R
O
wherein R14 and R,; have the saine meanings as groups R, to Rs, =,A,ith the proviso that groups R14 and R15 are omitted when the tin is divalent.
Also to be mentioned are metal carboxylates corresponding to formula (VI) R, s-COOM (VI), wherein R18 denotes a CI-C18 aliphatic or CS-C6 cyc.loaliphatic alkyl group or a C6-Ci() aryl group and M denotes an alkali metal, in particular sodium or potassium.
,f),-i;o to I-)e rnemioiied are hvdl-oxvl-containii7a arnines co1-responding to forn-Iula (V11) R,s-, N-R-N~R21 {VII~) or R's~N-R-O-R-N~R21 (VIIb) or R1 ~N-R22 iVIIC) ?(i V' 1l ~ I"G717 }:,,:; to tl;e sanie m anin<<s as groups R; to P. alid RC 206-Foreign Countries R22 denotes hydroxyethyl.
The following are particularly suitable compounds corresponding to formulae (I) to (VII):
N,N,N',N",N"-pentamethyldiethylenetriamine (I), N,N-dimethylbenzylamine (I), N,N-dimethylcyclohexylamine (I), M-methylmorpholine (I), bis(2-dimethylaminoethyl) ether (II), bis(2-morpholinoethyl) ether (II), 1,5-diazabicyclo[4.3.0]non-5-ene (III), 1,8-diazabicyclo[5.4.0]undec-7-ene (III), 2,3-dimethyl-3,4,5,6-tetrahydro-1,3-diazine (III), 1,4-diazabicyclo[2.2.2]octane (IV), tin(II) dioctanoate (V), tin(II) dipalmitate (V), di-n-butyltin(IV) dilaurate (V), potassium acetate (VI), potassium 2-ethylhexanoate (VI), N,N-dimethylaminoethoxyethanol (VII), (N,N-dimethylaminoethyl)-(N'-hydroxyethyl-N'-methylaminoethyl)ether (VII).
The following are particularly preferred:
1,5-diazabicyclo[4.3.0]non-5-ene (III), 1,4-diazabicyclo[2.2.2]octane (IV), di-n-butyltin(IV) dilaurate (V), tin(II) dioctanoate (V), potassium octanoate (VI), N,N-dimethylaminoethanol (VII).
Sterically hindered carbodiimides used according to the invention include those corresponding to formula (VIII) R23-N=C=N-R24 (VIII), wherein R23 and R24 are identical or different and denote iso-Propyl tert.-Butyl or I lo~( iso-Propyl tert.-Butyl Sterically hindered carbodiimides corresponding to formula (IX) are also suitable X-(-R25-N=C=N-R25-),,-X (IX), wherein X = -NCO, -NH-CO-Z-R26, iso-Propyl iso-Propyl =
iso-Propyl iso-Propyl iso-Propyl Me Me Me Me or iso-Propyl iso-Propyl RC 206-Foreign Countries R26 = Ct-C1g-alkyl, -aryl, -arylalkyl, -alkylenoxyalkyl, -alkoxypolyoxyalkylene Z= O,NH,S, n= 2 to 100.
Sterically hindered carbodiimides corresponding to the following formulae are particularly preferred iso-Propyl so-Propyl iso-Propyl OCN N C N N C N NCO
iso-Propyl iso-Propyl i-Prop. iso-Propyl i-Prop. iso-Propyl n or Me Me Me Me Me Me Me e Me Me Me ~e OCN N C [N-'->N=C_I N NCO
n wherein n= 2to100.
The following is most preferred:
Me Me Me Me Me Me e Me Me Me e Me OCN N C N
n wherein RC 206-Foreign Countries n = 2 to 100.
Both the previously mentioned PU catalysts and the sterically hindered carbodi-imides may be used individually or mixed with one another; the most favorable mixing ratio for this can be easily determined by appropriate preliminary experi-ments.
The sterically hindered carbodiimides used according to the present invention are known and are described, for example, in EP 062 854, DE 1 494 009, DE 2 020 330, DE 1 285 747, DE 2 248 751, EP 0 460 481 and US 5,246,993.
It is useful to add the catalyst system according to the present invention before the addition to the liquid components of the PU system in dissolved form, provided that the catalyst system according to the present invention is not already in liquid form.
Suitable solvents are particularly those which are used as components in the production of polyurethane; these can be water, polyols, isocyanates, polyisocyana-tes, blowing agents, plasticizers and foam stabilizers (silicone emulsifiers).
The suitable amount of solvent can be easily determined by appropriate preliminary experiments.
The catalyst system according to the invention is suitable for the production of many different kinds of PU materials, in particular for the production of flexible PU foams and integral PU foams.
The present invention therefore also provides the use of the catalyst systems according to the present invention for the production of PU materials, in particular of flexible PU foams and integral PU foams.
The invention is further illustrated but is not intended to be limited by the following examples in which all parts and percentages are by weight unless otherwise specified.
RC 206-Foreign Countries EXAMPLES
Example 1 (Preparation of a sterically hindered carbodiimide of the structure IX, with R25 = 1,3-bis(1-methylethyl) and X=-NH-CO-O-R26 with R26 = alkoxypolyoxyalkylene).
750 parts by weight (3.1 mol) 1,3-bis(l-methyl-2-isocyanatoethyl)-benzene having an NCO content of 34.4 wt.% was heated to 180 C in the presence of 1.5 parts by weight 1-methyl-2-phospholene-l-oxide and condensed at this temperature, with release of carbon dioxide. A reaction time of 23 hours was required to attain an NCO
content of 9.3 wt.%. Then 957 parts by weight of a methoxypolyoxyethylene alcohol having an average molecular weight (number average) of 520 g/mol was added, with stirring.
At a reaction temperature held constant at 180 C, the terminal NCO groups of the polymer chains were converted into urethane groups within a period of 30 minutes.
Then the 1-methyl-2-phospholene-l-oxide added as catalyst and the rest of the unreacted 1,3-bis(1-methyl-2-isocyanatoethyl)benzene were distilled off at a tem-perature of 190 C and at a pressure of 0.5 mbar.
1576 parts by weight of a mixture was obtained; the mixture was free from NCO
groups and consisted of monomeric and oligomeric polycarbodiimides having terminal methoxypolyoxyethylene-urethane groups. These polycarbodiimides had a content of N=C=N groups of 50 mg/g, a viscosity, as measured at 25 C by Ubbelohde's method, of 1950 mPa=s and an iodine colour index, measured after dilution with monochlorobenzene in the volume ratio of 1:5, of 2.4.
The mixture was very soluble in water.
RC 206-Foreign Countries The structure of the mixture of monomeric and oligomeric polycarbodiimides containing urethane groups was identified by 'H-NMR and the IR spectrum.
Structure of the carbodiimide in Example 1:
CH O-CHZ CHz N \ N=C=N ~O CH-CH-O H
I
N 2 z C 3 / I / H tt Examples 2 - 4 (Formulations) Example 2 3 4 * 1 Desmophen 2220 B Parts by wt. 100 100 100 Desmophen 2200 B
Desmodur T80 Water (total) Parts by wt. 4.50 4.50 4.50 Water (initially weighed) Parts by wt. - 3.50 3.50 *2 Stabilizer SE 232 Parts by wt. 1.00 1.00 1.00 *3 Desmorapid DB Parts by wt. 0.50 0.50 0.50 *3 RC PU activator 101 Parts by wt. 0.50 0.50 0.50 *3 RC PU activator 105 Parts by wt. 0.50 0.50 0.50 *4 Stabaxol P 200/H20 1/1 Parts by wt. - 1.00 1.00 Desmodur T80 Parts by wt. 54.00 54.00 54.00 Characteristic value 100 100 100 Temperature Desmophen/Desmodur ( C) 22/23 22/23 22/23 Pressure in mixing chamber (bar) 1.40 1.40 1.20 Belt speed (m miri ) 2.40 2.20 2.20 Example 2 ~ 4 ---------~ ----- -- ---- -- - -- - - _ ~ -----Delivery rate of (kL, min-) 22 22 22 Startingtime (s) 14 12 ]3 Rising tiliie (s) 63 62 62 Setting time (s) 33 45 45 *1 Desmoplien 2200 B
Desmodui- T80 => commercial product of Bayer AG
*2 Stabilizer SE 232 is a commercial product of the Witco Corporation TM
*3 Desmorapid DB, RC PU activator 101/RC PU activator 105 are commercial products of R11ein Chemie Rheinau GmbH
*4 Substaiice from Example 1, diluted 1:1 with water Desmodur T80tDR = 80% 2,4-tolylene diisocvanate = 20% 2,6-tolylene diisocyanate Stabaaol P2009 = highly polymeric carbodiimide fp. 80-100 C
RC PU acti\!ato~~~_'-, 1(_15 = 33" ~ triethylenediamine = 66 4, propylene ,1yc.o1 RC PU acti\,atorl~10] _ ?~' 1 ethylmorpholine Desmorapid DB din;ethvlbenz~laniine Desmopli:.=n, 22120 B = pol., ester polvol for flexible bloc.k foams n-iainl,, for t:;clinical at licles RC 206-Foreign Countries Examples 2 to 4 Aging test on the formulations, in accordance with DIN 53 578 120 h, 90 C, 90-95% Lf (Ford test) Description 2 3 4 Pressure test kPa 5.35 5.33 5.26 40% compression 5.29 5.23 5.08 Pressure test kPa 3.02 3.41 3.32 after storage Change in the % -44 -36 -37 pressure test Compression set 50% compression Blank value % 4.0 4.5 4.7 after storage 22.4 9.8 9.7 Tensile strength Blank value kPa 183 184 178 after storage kPa The results show that the foams containing sterically hindered carbodiimides and amines (3 + 4) have a significantly better compression set than those lacking the sterically hindered carbodiimide (2).
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that RC 206-Foreign Countries variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
All the known basic, as well as the electrophilic catalysts, which favor the formation of polyurethane al-e suitable as catalysts for the NCO/ON reaction. Such catalysts are described, for ey.ample, in Kunststoff-Handbuch, Volume 7, Polyurethane, Third newly revised Edition, Carl Hanser Verlag, Munich, Vierula, 1993, pp. 104 to 110.
Catalysts such as those described on page 105 of the above-mentioned publication are particularly suitable.
Such catalysts are, i.n particular (cyclo) aliphatic tertiary amines corresponding to the formulae (I) , R~Pv-?r [N-Rm] j N~R4 ~s . ) R ~a c~ N~ r,z wi;e, cin R denotes C, -C6 alkylene groups, R, to Rt are identical or diffei-ent and denote C1-C., alkyl, CS-C7 cycloalkyl, C(,-C,() aryl and C(,-C,(, arylmethyl or wherein groups Ri and R, and/or R~ and R4 can be bonded to one anotber via C,-C-, alkvlene ('roups c.ontaining 0 to 2 hetero atoms, such as nitro(,en, sulfur or ox~~~~eii, in the car-bon chain, n denotus inte,_,ers from 2 to 6, nl denotes lile nur7-ibers ? and ', and RC 206-Foreign Countries 1 denotes integers from 0 to 4.
Also to be mentioned are (cyclo)aliphatic aminoethers corresponding to formula (II) R6~N-R-O-R-N~R8 (II), R' Rg wherein R6 to Ry have the same meanings as groups Rl to R5 and R denotes C1-C6 alkylene groups.
Also to be mentioned are (cyclo)aliphatic amidines corresponding to formula (III) R10(-, N-C=N-R,a R" R' 2 (III), wherein Rlo to R13 have the same meanings as groups Rl to R5 or Rto and R13 and/or Rll and R12 can be bonded to one another via C2-C5 alkylene groups.
Also to be mentioned are bicyclic diamines corresponding to formula (IV) R
\N
R /
N\
R
(IV), wherein R has the same meaning as R in formula (II).
Also to be mentioned ai-e organotin compounds correspondinL, to fornnula (V) O
0 R,s Sn R1 \ R
O
wherein R14 and R,; have the saine meanings as groups R, to Rs, =,A,ith the proviso that groups R14 and R15 are omitted when the tin is divalent.
Also to be mentioned are metal carboxylates corresponding to formula (VI) R, s-COOM (VI), wherein R18 denotes a CI-C18 aliphatic or CS-C6 cyc.loaliphatic alkyl group or a C6-Ci() aryl group and M denotes an alkali metal, in particular sodium or potassium.
,f),-i;o to I-)e rnemioiied are hvdl-oxvl-containii7a arnines co1-responding to forn-Iula (V11) R,s-, N-R-N~R21 {VII~) or R's~N-R-O-R-N~R21 (VIIb) or R1 ~N-R22 iVIIC) ?(i V' 1l ~ I"G717 }:,,:; to tl;e sanie m anin<<s as groups R; to P. alid RC 206-Foreign Countries R22 denotes hydroxyethyl.
The following are particularly suitable compounds corresponding to formulae (I) to (VII):
N,N,N',N",N"-pentamethyldiethylenetriamine (I), N,N-dimethylbenzylamine (I), N,N-dimethylcyclohexylamine (I), M-methylmorpholine (I), bis(2-dimethylaminoethyl) ether (II), bis(2-morpholinoethyl) ether (II), 1,5-diazabicyclo[4.3.0]non-5-ene (III), 1,8-diazabicyclo[5.4.0]undec-7-ene (III), 2,3-dimethyl-3,4,5,6-tetrahydro-1,3-diazine (III), 1,4-diazabicyclo[2.2.2]octane (IV), tin(II) dioctanoate (V), tin(II) dipalmitate (V), di-n-butyltin(IV) dilaurate (V), potassium acetate (VI), potassium 2-ethylhexanoate (VI), N,N-dimethylaminoethoxyethanol (VII), (N,N-dimethylaminoethyl)-(N'-hydroxyethyl-N'-methylaminoethyl)ether (VII).
The following are particularly preferred:
1,5-diazabicyclo[4.3.0]non-5-ene (III), 1,4-diazabicyclo[2.2.2]octane (IV), di-n-butyltin(IV) dilaurate (V), tin(II) dioctanoate (V), potassium octanoate (VI), N,N-dimethylaminoethanol (VII).
Sterically hindered carbodiimides used according to the invention include those corresponding to formula (VIII) R23-N=C=N-R24 (VIII), wherein R23 and R24 are identical or different and denote iso-Propyl tert.-Butyl or I lo~( iso-Propyl tert.-Butyl Sterically hindered carbodiimides corresponding to formula (IX) are also suitable X-(-R25-N=C=N-R25-),,-X (IX), wherein X = -NCO, -NH-CO-Z-R26, iso-Propyl iso-Propyl =
iso-Propyl iso-Propyl iso-Propyl Me Me Me Me or iso-Propyl iso-Propyl RC 206-Foreign Countries R26 = Ct-C1g-alkyl, -aryl, -arylalkyl, -alkylenoxyalkyl, -alkoxypolyoxyalkylene Z= O,NH,S, n= 2 to 100.
Sterically hindered carbodiimides corresponding to the following formulae are particularly preferred iso-Propyl so-Propyl iso-Propyl OCN N C N N C N NCO
iso-Propyl iso-Propyl i-Prop. iso-Propyl i-Prop. iso-Propyl n or Me Me Me Me Me Me Me e Me Me Me ~e OCN N C [N-'->N=C_I N NCO
n wherein n= 2to100.
The following is most preferred:
Me Me Me Me Me Me e Me Me Me e Me OCN N C N
n wherein RC 206-Foreign Countries n = 2 to 100.
Both the previously mentioned PU catalysts and the sterically hindered carbodi-imides may be used individually or mixed with one another; the most favorable mixing ratio for this can be easily determined by appropriate preliminary experi-ments.
The sterically hindered carbodiimides used according to the present invention are known and are described, for example, in EP 062 854, DE 1 494 009, DE 2 020 330, DE 1 285 747, DE 2 248 751, EP 0 460 481 and US 5,246,993.
It is useful to add the catalyst system according to the present invention before the addition to the liquid components of the PU system in dissolved form, provided that the catalyst system according to the present invention is not already in liquid form.
Suitable solvents are particularly those which are used as components in the production of polyurethane; these can be water, polyols, isocyanates, polyisocyana-tes, blowing agents, plasticizers and foam stabilizers (silicone emulsifiers).
The suitable amount of solvent can be easily determined by appropriate preliminary experiments.
The catalyst system according to the invention is suitable for the production of many different kinds of PU materials, in particular for the production of flexible PU foams and integral PU foams.
The present invention therefore also provides the use of the catalyst systems according to the present invention for the production of PU materials, in particular of flexible PU foams and integral PU foams.
The invention is further illustrated but is not intended to be limited by the following examples in which all parts and percentages are by weight unless otherwise specified.
RC 206-Foreign Countries EXAMPLES
Example 1 (Preparation of a sterically hindered carbodiimide of the structure IX, with R25 = 1,3-bis(1-methylethyl) and X=-NH-CO-O-R26 with R26 = alkoxypolyoxyalkylene).
750 parts by weight (3.1 mol) 1,3-bis(l-methyl-2-isocyanatoethyl)-benzene having an NCO content of 34.4 wt.% was heated to 180 C in the presence of 1.5 parts by weight 1-methyl-2-phospholene-l-oxide and condensed at this temperature, with release of carbon dioxide. A reaction time of 23 hours was required to attain an NCO
content of 9.3 wt.%. Then 957 parts by weight of a methoxypolyoxyethylene alcohol having an average molecular weight (number average) of 520 g/mol was added, with stirring.
At a reaction temperature held constant at 180 C, the terminal NCO groups of the polymer chains were converted into urethane groups within a period of 30 minutes.
Then the 1-methyl-2-phospholene-l-oxide added as catalyst and the rest of the unreacted 1,3-bis(1-methyl-2-isocyanatoethyl)benzene were distilled off at a tem-perature of 190 C and at a pressure of 0.5 mbar.
1576 parts by weight of a mixture was obtained; the mixture was free from NCO
groups and consisted of monomeric and oligomeric polycarbodiimides having terminal methoxypolyoxyethylene-urethane groups. These polycarbodiimides had a content of N=C=N groups of 50 mg/g, a viscosity, as measured at 25 C by Ubbelohde's method, of 1950 mPa=s and an iodine colour index, measured after dilution with monochlorobenzene in the volume ratio of 1:5, of 2.4.
The mixture was very soluble in water.
RC 206-Foreign Countries The structure of the mixture of monomeric and oligomeric polycarbodiimides containing urethane groups was identified by 'H-NMR and the IR spectrum.
Structure of the carbodiimide in Example 1:
CH O-CHZ CHz N \ N=C=N ~O CH-CH-O H
I
N 2 z C 3 / I / H tt Examples 2 - 4 (Formulations) Example 2 3 4 * 1 Desmophen 2220 B Parts by wt. 100 100 100 Desmophen 2200 B
Desmodur T80 Water (total) Parts by wt. 4.50 4.50 4.50 Water (initially weighed) Parts by wt. - 3.50 3.50 *2 Stabilizer SE 232 Parts by wt. 1.00 1.00 1.00 *3 Desmorapid DB Parts by wt. 0.50 0.50 0.50 *3 RC PU activator 101 Parts by wt. 0.50 0.50 0.50 *3 RC PU activator 105 Parts by wt. 0.50 0.50 0.50 *4 Stabaxol P 200/H20 1/1 Parts by wt. - 1.00 1.00 Desmodur T80 Parts by wt. 54.00 54.00 54.00 Characteristic value 100 100 100 Temperature Desmophen/Desmodur ( C) 22/23 22/23 22/23 Pressure in mixing chamber (bar) 1.40 1.40 1.20 Belt speed (m miri ) 2.40 2.20 2.20 Example 2 ~ 4 ---------~ ----- -- ---- -- - -- - - _ ~ -----Delivery rate of (kL, min-) 22 22 22 Startingtime (s) 14 12 ]3 Rising tiliie (s) 63 62 62 Setting time (s) 33 45 45 *1 Desmoplien 2200 B
Desmodui- T80 => commercial product of Bayer AG
*2 Stabilizer SE 232 is a commercial product of the Witco Corporation TM
*3 Desmorapid DB, RC PU activator 101/RC PU activator 105 are commercial products of R11ein Chemie Rheinau GmbH
*4 Substaiice from Example 1, diluted 1:1 with water Desmodur T80tDR = 80% 2,4-tolylene diisocvanate = 20% 2,6-tolylene diisocyanate Stabaaol P2009 = highly polymeric carbodiimide fp. 80-100 C
RC PU acti\!ato~~~_'-, 1(_15 = 33" ~ triethylenediamine = 66 4, propylene ,1yc.o1 RC PU acti\,atorl~10] _ ?~' 1 ethylmorpholine Desmorapid DB din;ethvlbenz~laniine Desmopli:.=n, 22120 B = pol., ester polvol for flexible bloc.k foams n-iainl,, for t:;clinical at licles RC 206-Foreign Countries Examples 2 to 4 Aging test on the formulations, in accordance with DIN 53 578 120 h, 90 C, 90-95% Lf (Ford test) Description 2 3 4 Pressure test kPa 5.35 5.33 5.26 40% compression 5.29 5.23 5.08 Pressure test kPa 3.02 3.41 3.32 after storage Change in the % -44 -36 -37 pressure test Compression set 50% compression Blank value % 4.0 4.5 4.7 after storage 22.4 9.8 9.7 Tensile strength Blank value kPa 183 184 178 after storage kPa The results show that the foams containing sterically hindered carbodiimides and amines (3 + 4) have a significantly better compression set than those lacking the sterically hindered carbodiimide (2).
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that RC 206-Foreign Countries variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
Claims (20)
1. A catalyst system for a polyurethane formation, NCO/OH, reaction, comprising:
(A) at least one catalyst for the polyurethane formation, NCO/OH, reaction; and (B) at least one sterically hindered carbodiimide, wherein component (B) is present in a quantity of 1 wt.% up to 200 wt.%, based on the total quantity of component (A).
(A) at least one catalyst for the polyurethane formation, NCO/OH, reaction; and (B) at least one sterically hindered carbodiimide, wherein component (B) is present in a quantity of 1 wt.% up to 200 wt.%, based on the total quantity of component (A).
2. A catalyst system according to claim 1, wherein (A) is a compound of the general formula (Ia):
wherein:
R represents C1-C6 alkylene;
R1 to R5 are identical or different and represent C1-C18 alkyl, C5-C7 cycloalkyl, C6-C10 aryl or C6-C10 arylmethyl, or R1 and R2 and/or R3 and R4 are bonded to one another via a C2-C5 alkylene group containing 0 to 2 hetero atoms in the carbon chain, n is an integer from 2 to 6;
m is 2 or 3; and l is an integer from 0 to 4.
wherein:
R represents C1-C6 alkylene;
R1 to R5 are identical or different and represent C1-C18 alkyl, C5-C7 cycloalkyl, C6-C10 aryl or C6-C10 arylmethyl, or R1 and R2 and/or R3 and R4 are bonded to one another via a C2-C5 alkylene group containing 0 to 2 hetero atoms in the carbon chain, n is an integer from 2 to 6;
m is 2 or 3; and l is an integer from 0 to 4.
3. A catalyst according to claim 2, wherein the hetero atoms are nitrogen, sulfur or oxygen.
4. A catalyst system according to claim 1, wherein (A) is a compound of the general formula (Ib):
wherein R1 to R3 are identical or different and represent C1-C18 alkyl, C5-C7 cycloalkyl, C6-C10 aryl or C6-C10 arylmethyl, or R1 and R2 and/or R3 are bonded to one another via a C2-C5 alkylene group containing 0 to 2 hetero atoms in the carbon chain.
wherein R1 to R3 are identical or different and represent C1-C18 alkyl, C5-C7 cycloalkyl, C6-C10 aryl or C6-C10 arylmethyl, or R1 and R2 and/or R3 are bonded to one another via a C2-C5 alkylene group containing 0 to 2 hetero atoms in the carbon chain.
5. A catalyst according to claim 4, wherein the hetero atoms are nitrogen, sulfur or oxygen.
6. A catalyst system according to claim 1, wherein (A) is a compound of the general formula (II):
wherein:
R represents C1-C6 alkylene; and R6 to R9 are identical or different and represent C1-C18 alkyl, C5-C7 cycloalkyl, C6-C10 aryl or C6-C10 arylmethyl; or R6 and R7 and/or R8 and R9 are bonded to one another via a C2-C5 alkylene group containing 0 to 2 hetero atoms in the carbon chain.
wherein:
R represents C1-C6 alkylene; and R6 to R9 are identical or different and represent C1-C18 alkyl, C5-C7 cycloalkyl, C6-C10 aryl or C6-C10 arylmethyl; or R6 and R7 and/or R8 and R9 are bonded to one another via a C2-C5 alkylene group containing 0 to 2 hetero atoms in the carbon chain.
7. A catalyst system according to claim 1, wherein (A) is a compound of the general formula (III):
wherein:
R10 to R13 are identical or different and represent C1-C18 alkyl, C5-C7 cycloalkyl, C6-C10 aryl or C6-C10 arylmethyl; or R10 and R13 and/or R11 and R12 are bonded to one another via a C2-C5 alkylene group.
wherein:
R10 to R13 are identical or different and represent C1-C18 alkyl, C5-C7 cycloalkyl, C6-C10 aryl or C6-C10 arylmethyl; or R10 and R13 and/or R11 and R12 are bonded to one another via a C2-C5 alkylene group.
8. A catalyst system according to claim 1, wherein (A) is a compound of the general formula (IV):
wherein R represents C1-C6 alkylene.
wherein R represents C1-C6 alkylene.
9. A catalyst system according to claim 1, wherein (A) is a compound of the general formula (VI):
R18-COOM (VI) wherein:
R18 represents a C1-C18 aliphatic or C5-C6 cycloaliphatic alkyl group or a C6-C10 aryl group; and M represents an alkali metal.
R18-COOM (VI) wherein:
R18 represents a C1-C18 aliphatic or C5-C6 cycloaliphatic alkyl group or a C6-C10 aryl group; and M represents an alkali metal.
10. A catalyst system according to claim 9, wherein the alkali metal is sodium or potassium.
11. A catalyst system according to claim 1, wherein (A) is a compound of the general formula (VIIa):
wherein:
R represents C1-C6 alkylene;
R19 to R21 are identical or different and represent C1-C18 alkyl, C5-C7 cycloalkyl, C6-C10 aryl or C6-C10 arylmethyl; or R19 and R20 are bonded to one another via a C2-C5 alkylene group containing 0 to 2 hetero atoms in the carbon chain;
and R22 represents hydroxyethyl.
wherein:
R represents C1-C6 alkylene;
R19 to R21 are identical or different and represent C1-C18 alkyl, C5-C7 cycloalkyl, C6-C10 aryl or C6-C10 arylmethyl; or R19 and R20 are bonded to one another via a C2-C5 alkylene group containing 0 to 2 hetero atoms in the carbon chain;
and R22 represents hydroxyethyl.
12. A catalyst system according to claim 1, wherein (A) is a compound of the general formula (VIIb):
wherein R and R19 to R22 are as defined in claim 11.
wherein R and R19 to R22 are as defined in claim 11.
13. A catalyst system according to claim 1, wherein (A) is a compound of the general formula (VIIc):
wherein R19, R20 and R22 are as defined in claim 11.
wherein R19, R20 and R22 are as defined in claim 11.
14. A catalyst system according to any one of claims 1 to 13, wherein (B) is a compound of the general formula (VIII):
R23-N=C=N-R24 (VIII), wherein R23 and R24 are identical or different and represent:
R23-N=C=N-R24 (VIII), wherein R23 and R24 are identical or different and represent:
15. A catalyst system according to any one of claims 1 to 13, wherein (B) is a compound of the general formula (IX):
X-(-R25-N=C=N-R25-)n-X (IX) wherein:
X represents -NCO or -NH-CO-Z-R26;
R25 represents R26 represents C1-C18-alkyl, -aryl, -arylalkyl, -alkylenoxyalkyl or -alkoxypolyoxyalkylene;
Z represents O, NH or S; and n = 2 to 100.
X-(-R25-N=C=N-R25-)n-X (IX) wherein:
X represents -NCO or -NH-CO-Z-R26;
R25 represents R26 represents C1-C18-alkyl, -aryl, -arylalkyl, -alkylenoxyalkyl or -alkoxypolyoxyalkylene;
Z represents O, NH or S; and n = 2 to 100.
16. A catalyst system according to any one of claims 1 to 13, wherein (B) is a compound of the general formula:
wherein n = 2 to 100.
wherein n = 2 to 100.
17. A catalyst system according to any one of claims 1 to 13, wherein (B) is a compound of the general formula:
wherein n = 2 to 100.
wherein n = 2 to 100.
18. A process for preparing a polyurethane material comprising reacting an isocyanate-containing material with a hydroxyl-containing material in the presence of a catalyst system according to any one of claims 1 to 17.
19. A process according to claim 18, for preparing a flexible polyurethane foam.
20. A process according to claim 18, for preparing an integral polyurethane foam.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19930556.0 | 1999-07-02 | ||
| DE19930556 | 1999-07-02 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2313256A1 CA2313256A1 (en) | 2001-01-02 |
| CA2313256C true CA2313256C (en) | 2009-06-02 |
Family
ID=7913430
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002313256A Expired - Fee Related CA2313256C (en) | 1999-07-02 | 2000-06-29 | Catalyst system for the nco/oh reaction (polyurethane formation) |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US6602926B1 (en) |
| EP (1) | EP1065237B1 (en) |
| JP (1) | JP4559592B2 (en) |
| AT (1) | ATE253096T1 (en) |
| CA (1) | CA2313256C (en) |
| DE (1) | DE50004222D1 (en) |
| ES (1) | ES2208185T3 (en) |
| NO (1) | NO20003420L (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8258198B2 (en) * | 2004-05-28 | 2012-09-04 | Air Products And Chemicals, Inc. | Fast demold/extended cream time polyurethane formulations |
| PT2315807E (en) | 2008-08-20 | 2012-09-03 | Rhein Chemie Corp | Polyol compositions |
| RU2014153664A (en) * | 2012-06-05 | 2016-07-27 | Райн Хеми Райнау ГмбХ | CONTAINING CARBODYMIDES OF THE COMPOSITION OF A NEW TYPE, METHOD FOR PRODUCING THEM AND THEIR APPLICATION |
| CA2989239C (en) * | 2015-06-15 | 2023-07-11 | Lanxess Deutschland Gmbh | Method for the synthesis of polymer carbodiimides with added cesium salts, polymer carbodiimides, use thereof |
| CN112898524A (en) * | 2021-02-18 | 2021-06-04 | 南通诺世环保科技有限公司 | Preparation method of polyurethane environment-friendly catalyst in application of sponge material |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1310138A (en) | 1960-12-02 | 1963-03-06 | ||
| NL273087A (en) | 1960-12-31 | |||
| DE2020330A1 (en) | 1970-04-25 | 1971-11-11 | Glanzstoff Ag | Process to improve the stability of polyesters |
| CA987042A (en) | 1971-10-05 | 1976-04-06 | General Tire And Rubber Company (The) | Method for making urethane-terminated polycarbodiimides and products thereof |
| US4113676A (en) * | 1977-05-31 | 1978-09-12 | Ppg Industries, Inc. | Aqueous dispersions of esters stabilized with carbodiimides |
| US4849470A (en) * | 1988-10-31 | 1989-07-18 | Advanced Protection Technologies, Inc. | Polyurethane systems especially adapted for surge suppression |
| DE4018184A1 (en) * | 1990-06-07 | 1991-12-12 | Bayer Ag | METHOD FOR STABILIZING PLASTICS CONTAINING ESTER GROUPS |
| DE4126359A1 (en) | 1991-08-09 | 1993-02-11 | Basf Ag | OLIGOMER CARBODIIMIDES |
| DE4238046A1 (en) * | 1992-11-11 | 1994-05-19 | Basf Ag | New bis (4-substituted-2,6-diisopropylphenyl) carbodiimides, a process for their preparation and their use and the 4-substituted 2,6-diisopropylphenyl isocyanates which can be used for their preparation |
| DE19548771A1 (en) * | 1995-12-23 | 1997-06-26 | Basf Ag | Microcellular polyurethane elastomer containing urea groups |
| DE19548770A1 (en) * | 1995-12-23 | 1997-06-26 | Basf Ag | Microcellular polyurethane elastomer containing urea groups |
| JP3733170B2 (en) * | 1996-04-02 | 2006-01-11 | 日清紡績株式会社 | Polyurethane resin |
| DE19627907A1 (en) * | 1996-07-11 | 1998-01-15 | Basf Ag | Process for the production of compact or cellular polyurethane elastomers and isocyanate prepolymers suitable for this |
| DE19821666A1 (en) * | 1998-05-14 | 1999-11-25 | Basf Ag | Carbo-di:imide compounds, useful as hydrolytic stabilisers, especially for polyurethane elastomers containing ester units |
| US6063890A (en) * | 1998-07-01 | 2000-05-16 | Basf Corporation | Polycarbodiimide polymers and their use as adhesive intermediate layers in automotive coatings |
-
2000
- 2000-06-23 DE DE50004222T patent/DE50004222D1/en not_active Expired - Lifetime
- 2000-06-23 AT AT00113048T patent/ATE253096T1/en not_active IP Right Cessation
- 2000-06-23 EP EP00113048A patent/EP1065237B1/en not_active Expired - Lifetime
- 2000-06-23 ES ES00113048T patent/ES2208185T3/en not_active Expired - Lifetime
- 2000-06-26 US US09/602,858 patent/US6602926B1/en not_active Expired - Lifetime
- 2000-06-29 CA CA002313256A patent/CA2313256C/en not_active Expired - Fee Related
- 2000-06-30 NO NO20003420A patent/NO20003420L/en not_active Application Discontinuation
- 2000-07-03 JP JP2000200959A patent/JP4559592B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EP1065237A1 (en) | 2001-01-03 |
| EP1065237B1 (en) | 2003-10-29 |
| DE50004222D1 (en) | 2003-12-04 |
| JP4559592B2 (en) | 2010-10-06 |
| US6602926B1 (en) | 2003-08-05 |
| ATE253096T1 (en) | 2003-11-15 |
| JP2001031735A (en) | 2001-02-06 |
| NO20003420L (en) | 2001-01-03 |
| NO20003420D0 (en) | 2000-06-30 |
| CA2313256A1 (en) | 2001-01-02 |
| ES2208185T3 (en) | 2004-06-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3236348B2 (en) | Process for the production of liquid storable organic isocyanates containing carbodiimide and / or uretonimine groups and their use for the production of polyurethane plastics | |
| CA2042004C (en) | Process for the production of isocyanurate polyisocyanates, the compounds obtained by this process and their use | |
| KR0141440B1 (en) | Quaternary ammonium carboxylate inner salt compositions as controlled activity catalysts for making polyurethane foam | |
| CA1126894A (en) | Process for the preparation of organopolysiloxanes | |
| US6498225B2 (en) | Polycarbodiimide-based block copolymers, a method of preparing them and their use as hydrolysis stabilizers | |
| US20070155937A1 (en) | Process for the preparation of liquid, storage-stable organic isocyanates containing carbodiimide and/or uretoneimine groups | |
| US3203932A (en) | Metallo-organic catalyzed one-shot process for preparing urethaneurea elastomers | |
| KR100296482B1 (en) | 4-substituted bis (2,6-diisopropylphenyl) carbodiimide, methods for their preparation, their use, and 4-substituted 2,6-diisopropylphenyl isocyanate used in their preparation | |
| EP0844276B1 (en) | Reactivity stabilization of polymethylene poly(phenylisocyanates) | |
| CA2313256C (en) | Catalyst system for the nco/oh reaction (polyurethane formation) | |
| JPS59108025A (en) | Novel polyisocyanate mixture, manufacture and use as synthetic component for polyurethane plastic | |
| US6703471B2 (en) | Preparation of low-odor-storage-stable monomer-containing polyisocyanurates based on isophorone diisocyante | |
| EP1532186B1 (en) | Low emission tin catalysts | |
| US4076945A (en) | Method for making urethane-terminated polycarbodiimides and products thereof | |
| EP0060974B1 (en) | Amino and amidodiorgano tin carboxylates | |
| DE2914134A1 (en) | METHOD FOR PRODUCING POLYURETHANE FOAMS | |
| JPH0578439A (en) | Manufacture of polyisocyanate polyaddition product | |
| US4322364A (en) | Modified isocyanate compositions | |
| US3535359A (en) | Stabilization of organic isocyanates | |
| EP1431322B1 (en) | Stable polyol dispersions and the polyurethane moulded pieces prepared therefrom and their use | |
| US3766147A (en) | Condensation of cyclic nitrile carbonates with fluoride compounds | |
| JP3369279B2 (en) | Methods for conditioning and stabilizing polyols | |
| USRE38415E1 (en) | Use of N-(aminoalkyl) pyrrolidines as catalysts for the polyisocyanate polyaddition process | |
| EP0032011A1 (en) | Modified isocyanate compositions | |
| US3953384A (en) | Process for preparing polyurethane foams |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |
Effective date: 20180629 |