WO2010108307A1

WO2010108307A1 - Thermoplastically processable polyvinyl alcohol alloy and preparation method thereof

Info

Publication number: WO2010108307A1
Application number: PCT/CN2009/001212
Authority: WO
Inventors: 刘建林
Original assignee: Liu Jianlin
Priority date: 2009-03-25
Filing date: 2009-11-02
Publication date: 2010-09-30
Also published as: CN102361930A; CN102361930B; CN101845185A

Abstract

A polyvinyl alcohol alloy is provided, which consists essentially of about 5wt% ~ about 94.99wt% of polyvinyl alcohol homopolymer, about 75wt% ~ about 5wt% of polyamide, 0.01wt% ~ about 20wt% of heatstable inhibitor and 0 ~ about 20wt% of conventional additives chosen from plasticizer, light stabilizer and/or antioxidant. The polyvinyl alcohol alloy is suitable in the manufacture of high barrier product, such as multilayer co-extruded high barrier films or sheets, and the film has an air permeability in 24 hours of less than about 20 cm³/m²·24h·0.1MPa as measured by differential pressure measurement according to GB/T1038-2000.

Description

Thermoplastically processable polyvinyl alcohol alloy

The present invention claims priority to Chinese Patent Application No. 200910127,984, filed on March 25, 2009, which is incorporated herein by reference. Technical field

The present invention relates to a thermoplastically processable polyvinyl alcohol alloy, and in particular to a blend consisting essentially of a polyvinyl alcohol homopolymer, a polyamide, a thermal decomposition inhibitor, and a processing regulator, and Preparation. The polyephthyl alcohol alloy is suitable for thermoplastic processing into various high barrier films, sheets, tubes, hollow containers, etc., and the present invention also relates to the above products prepared from the polyvinyl alcohol alloy of the present invention. Background technique

Polyvinyl alcohol is a known polymer having very excellent high barrier properties. However, polyvinyl alcohol homopolymer (PVA) is not suitable for thermoplastic processing because its melting point is higher than the decomposition temperature. In particular, polyvinyl alcohol homopolymers having a degree of hydrolysis of about 99% are completely incapable of thermoplastic processing.

In order to improve the thermoplastic processing properties of polyvinyl alcohol homopolymers, ethylene-vinyl alcohol copolymer (EV0H) has been widely used. However, EV0H is very expensive. At the same time, due to the introduction of ethylene copolymerization unit, the mechanical strength of EV0H is significantly lower than that of polyvinyl alcohol homopolymer, which makes EV0H unsuitable as a high-resistance heat-insulating shrink film. Further, it is important that the barrier property of EV0H is remarkably lowered due to the introduction of the ethylene copolymerization unit, and the drop is particularly remarkable after moisture absorption. Therefore, EV0H is not satisfactory in many performances.

No. 4,952,628 discloses a blend of EVOH and polyamide. US 4,950,513 discloses PVA/nylon blends for use in combination with polyolefins. US Blends of nylon and EVOH are also disclosed in 4, 640, 852, 5, 055, 355, and the like.

The blends in the above documents all contain olefin units which are introduced by blending with a polyolefin or EVOH itself. Both of them significantly affect the barrier properties of the resulting article, and due to the high viscosity of the blend, it causes adhesion to the metal in the screw and the mold flow path in subsequent applications such as blown film, and thereby causes decomposition and carbonization of the raw material.

No. 4,611,019 discloses a melt-extrudable composition which consists essentially of a polyvinyl alcohol homopolymer, from 7% to 15% by weight of the polyvinyl alcohol homopolymer, selected from aromatic sulfonamides. , plasticizers of polyhydric alcohols, aromatic sulfonates, aromatic phosphates and phosphites, N, N-dimethylamides of carboxylic acids, alkylene carbonates, alkylpyrrolidone and mixtures thereof, and 5%-4. 5% of a molecular weight of 1,500 to 30,000, selected from the group consisting of nylon 66, nylon 6, nylon 11, nylon 12, nylon 6, 10 copolymer, a nylon 6,12 copolymer and a polyamide composition of grafted nylon, wherein the polyvinyl alcohol homopolymer has a degree of hydrolysis of greater than 95% and has a viscosity of 2 (TC 4% aqueous solution in the range of 2 to 30 centipoise) Molecular weight.

The melt-extrudable blends disclosed in this document include polyvinyl alcohol, small amounts of polyamide, and a large amount of plasticizer. 5wt°/。 By experiment, found that 0. 5wt ° /. - 4. 5 «^% of the mixture of the polyamide resin and the plasticizer used in this document does not plasticize the polyvinyl alcohol having a degree of hydrolysis of more than about 99%, so US 4,611, 019 has to use the degree of hydrolysis. The low hydrolysis degree polyvinyl alcohol is plasticized by about 95% of polyvinyl alcohol and using a large amount of a plasticizer. However, the use of such a large amount of plasticizer and the use of a lower degree of hydrolysis of polyvinyl alcohol pose serious problems. For example, their use can significantly reduce the barrier properties of materials, making them unable to meet high barrier requirements. In addition, the plasticizers used in US 4, 611, 019 are mostly small-molecule toxic substances, which limits their application fields. At the same time, because these materials are prone to irritating gases in thermoplastic processing, they are formed in thin films and the like. The bubbles remain, which in turn affects the barrier properties.

Therefore, there is still a need in the art to provide a polyvinyl alcohol-based material that maintains the high barrier properties and mechanical strength characteristic of polyvinyl alcohol homopolymers while satisfying Requirements for conventional thermoplastic processing. Summary of invention

In order to solve the above problems of the prior art, the inventors conducted extensive and intensive research, and unexpectedly found that by using the following polyvinyl alcohol alloy of the present invention, it is possible to maintain high barrier properties of polyvinyl alcohol and At the same time of mechanical strength, very excellent thermoplastic processing properties are obtained.

According to an aspect of the invention, a polyvinyl alcohol alloy is provided, which is substantially from about 53⁄4% to about 94.99wt. /. a polyvinyl alcohol homopolymer, about H 5 wt% polyamide, 0.01 wt% to 20 wt% of a thermal decomposition inhibitor, and 0 to about 20 wt% of a conventional additive (for example, a plasticizer, a light stabilizer, and/or Or antioxidant), based on the total weight of the polyvinyl alcohol alloy.

According to another aspect of the present invention, there is provided a method of producing a polyvinyl alcohol alloy, the method comprising: mixing the polyvinyl alcohol homopolymer, a polyamide, a thermal decomposition inhibitor, and a conventional additive (for example, Plasticizers, light stabilizers and/or antioxidants), the blends are thermoplastically processed and granulated.

According to still another aspect of the present invention, there is provided a product prepared from the polyvinyl alcohol alloy, including, but not limited to, a high barrier film, a hollow container, a tube, a sheet, and the like. Detailed description of the invention

In the following description of the present invention, the numerical values in the present application can be regarded as the word "about," modified, unless otherwise explicitly stated. However, the inventors have been as precise as possible in the examples. Numerical values, although these values inevitably include certain errors.

In the present application, specific or preferred embodiments of the invention may be combined unless explicitly excluded. In addition, each element of the embodiment of the present application is a corresponding upper level A specific preferred selection of technical features. If the superior technical feature can be combined with other superior features, the elements of the embodiment, ie the specific preferred selection, can also be combined with the other superior features. These combinations are considered to be part of the original description of this application.

In the present application, the term "consisting essentially of" means that the content of the unspecified component does not significantly or substantially affect the properties of the polyvinyl alcohol alloy of the present invention. The term "substantially free" means that the content of the impurities should be less than about 1% by weight or not at all. For example, in the present invention, the polyvinyl alcohol homopolymer is substantially free of ethylene copolymerized units, and the alloy is also substantially free of olefin blending components.

In the present application, the term "high barrier" means physical barrier to air, especially oxygen. Typically, the pressure is measured by the differential pressure method according to GB/T1038-2000, and the gas permeation amount is less than about 20 cm ³ /m ^{2 in} 24 hours. 24h-0. lMPa ₀

1重量°。 According to an aspect of the invention, a polyvinyl alcohol alloy, substantially from about 5% to about 94. 99wt% of a polyvinyl alcohol homopolymer, about w H 5wt% of polyamide, 0.011wt ° /. ~ 20% by weight of a thermal decomposition inhibitor and 0 to about 20% by weight of a conventional additive (e.g., a plasticizer, a light stabilizer, and/or an antioxidant), based on the total weight of the polyvinyl alcohol alloy.

According to one embodiment of the invention, the polyvinyl alcohol alloy consists essentially of about 53⁄4^/. ~ about 80 wt% of polyvinyl alcohol homopolymer, about 94.9 1% ~ about 5 wt% of polyamide, and about 0. ^1;% ~ about 15 ^ ^% of thermal decomposition inhibitor composition, based on polyethylene The total weight of the alcohol alloy is based on the total weight of the polyvinyl alcohol alloy.

According to another preferred embodiment, the polyvinyl alcohol alloy consists essentially of from about 25:1% to about 75% by weight of a polyvinyl alcohol homopolymer, from about 70% to about 23% by weight of polyamide, and from about 2% by weight to about 5 wt% of the thermal decomposition inhibitor composition, based on the total weight of the polyvinyl alcohol alloy.

According to still another preferred embodiment, the polyvinyl alcohol alloy is substantially comprised

5 重量% ~ 29. 5wt%聚聚 The amide and the composition of about 0.5% by weight to about 1.5% by weight of the thermal decomposition inhibitor, based on the total weight of the polyvinyl alcohol alloy.

According to another embodiment of the present invention, the polyvinyl alcohol alloy is substantially from about 15 wt% to about 84.8 wt% of a polyvinyl alcohol homopolymer, from about 55 wt% to about 15 wt% of a polyamide, About 0. ^1:°/. ~ about 10wt ° /. Thermal decomposition inhibitor and 0. ^1; ° /. ~about

20wt. /. The plasticizer, light stabilizer and/or antioxidant composition is based on the total weight of the polyvinyl alcohol alloy.

The polyvinyl alcohol homopolymer according to the present invention can be obtained from polyvinyl acetate by a conventional hydrolysis process, and its degree of hydrolysis is preferably at least about 88%, more preferably at least about 95%, and most preferably at least about 99%. The polyvinyl alcohol homopolymer may have a degree of polymerization of from about 500 to about 2,500, preferably from about 1,700 to about 2,000. The polyvinyl alcohol homopolymer of the present invention is substantially free of olefin copolymerized units such as ethylene.

Polyamides suitable for use in the present invention include those commonly referred to as nylons, including, but not limited to, nylon 6, nylon 66, nylon 11, nylon 1010, nylon 12, nylon 46, nylon 69, nylon, in accordance with a preferred embodiment of the present invention. 610, nylon 612, nylon 1212, nylon MXD6, nylon TMDT, copolymers and blends of the above nylons. The nylon may be an amorphous nylon, a nylon thermoplastic elastomer, and a nylon grafted with maleic anhydride, acrylic or epoxy. The most preferred polyamides are nylon 6, nylon 66 and mixtures thereof. The molecular weight of the polyamide can be about 10, 000-50, 000, melt flow index (of Ml) may be from about 1- 200g / 10min, preferably from about 15-100g / 10min _o

Thermal decomposition inhibitors suitable for use in the present invention include, but are not limited to, lactam monomers for forming nylon, such as caprolactam, decanolactam, etc., amino acids, nylon salts, aliphatic phosphates and phosphites, for example, preferably trimethyl phosphate Esters, triethyl phosphate, tributyl phosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, especially preferably trimethyl phosphate, triethyl phosphate, trimethyl phosphite and phosphorous acid Triethyl ester.

In the present invention, the term "conventional additive" means generally used for homopolymerization of polyvinyl alcohol. Additives in the processing of the substance or its copolymer, such as plasticizers, antioxidants, light stabilizers. The inventors have found that the use of these conventional additives alone, without the use of the above-mentioned heat stabilizers, especially aliphatic phthalates and phosphites, does not provide satisfactory thermoplastic processing properties and air barrier properties.

Plasticizers suitable for use in the present invention may include, but are not limited to, polyols such as glycerol, sorbitol, pentaerythritol, ethylene oxide, propylene oxide, ethylene glycol, poly, in accordance with embodiments of the present invention. Ethylene glycol, polypropylene glycol, glycol ether, propylene glycol ether, glyceryl ether, water, diethylene glycol, triethylene glycol, tetraethylene glycol, and mixtures thereof; alcohol amines such as ethanolamine, diethanolamine, triethanolamine, and a mixture; a carboxylic acid and a salt or ester thereof, such as citric acid, (meth)acrylic acid, dodecanoic acid, azelaic acid, sebacic acid, isophthalic acid, terephthalic acid, stearate, single hard Glycerol, dimer acid, tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoic acid] pentaerythritol ester, and mixtures thereof; amine, 1, 4-butanediamine, 1 , 6-hexanediamine, 4,4,-aminocyclohexane, and mixtures thereof; amides such as stearic acid amide, erucamide, oleic acid amide, hydrazine, hydrazine-dimethylacetamide, and mixtures thereof Aromatic phosphate or phosphite, such as triphenyl phosphate, sub Acid triphenyl phosphite, bisphenol Α phosphite, tris (nonylphenyl) phosphite, and mixtures thereof.

The polyvinyl alcohol alloy of the present invention may further contain a conventional light stabilizer as a conventional additive, such as benzophenone, UV-531, UV-242, BP-4, hindered amine, 788, UV-3034, 744. And one or more of the antioxidants; and/or antioxidants, such as hindered phenols: 1010, 3114, 330, 54 , and the sub-base acid esters: one or more of 168, 619, 618.

According to a specific embodiment of the present invention, a nano inorganic material, a colorant, a fragrance, an antibacterial agent or the like may be included as a conventional additive according to actual needs.

According to another aspect of the present invention, there is provided a method of producing a polyvinyl alcohol alloy, the method comprising: mixing the polyvinyl alcohol homopolymer, a polyamide, a thermal decomposition inhibitor, and the conventional additive, The blend is thermoplastically processed and granulated. According to a particular embodiment of the invention, the thermoplastic processing can be carried out by known thermoplastic processing methods such as internal mixers, single screw extruders, silent screw extruders, reactive vented single and twin screw extruders, and the like.

According to another aspect of the present invention, there is provided a product prepared from the polyvinyl alcohol alloy, including but not limited to, a high barrier film, a hollow container, a tube and a sheet, and the like. Preferably, the product may include, but is not limited to, a single layer film, a multi-layer co-extruded film, a high temperature cooking film, a joy-stretching film, a heat shrink film, an automobile fuel tank, a bottle, a barrel, a fuel or oil pipeline, and a gas pipe.

By comparing the data described in Table 2 of the examples, it is not difficult to see that the products prepared by the polyvinyl alcohol alloy of the present invention have better tensile strength and elongation at break than the mixture of EV0H and EVOH and PA, and It has excellent gas barrier properties and aroma retention. The inventors have also unexpectedly found that the alloy material has more excellent organic solvent resistance, oil resistance, and chemical resistance than pure polyethylene alone or pure polyamide resin alone. The Table 1 data also shows that the PVA content of the product of the invention is about 45 wt. /. When the PVA content is about 70wt%, the performance is unmatched by the prior art materials, and has very good processability, film formation, And processing thermal stability.

According to a specific embodiment of the present invention, the polyvinyl alcohol alloy material of the present invention is placed in an extrusion blown film machine under continuous processing conditions of about 170 ° C, 190 ° C, 210 ° C and 230 ° C, respectively. The film was extruded and extruded for about 100 hours without the material decomposing and not carbonizing, while having very excellent transparency.

According to a specific embodiment of the present invention, the polyvinyl alcohol alloy of the present invention is used as a barrier layer (thickness 5 μm) by using a five-layer co-extrusion apparatus, and a material such as polyethylene is used as another layer (thickness: 95 μm) to form a film. The oxygen permeation amount is less than about 1.2 cm ³ / m ² -24 h -0.1. IMPa is clearly superior to the same coextruded film of the ethylene-vinyl alcohol copolymer (EV0H) as a barrier layer.

According to a specific embodiment of the present invention, the polyvinyl alcohol alloy of the present invention can be made Multi-layer co-extruded high-resistance heat-shrinkable shrink film or biaxially stretched film, which are not suitable for ethylene-vinyl alcohol copolymer (EV0H).

By multi-layer coextrusion with other types of materials, such as polyethylene (PE), polypropylene (PP), polyester (PET), polyamide (PA), etc., it can be made of the polyvinyl alcohol alloy of the present invention. High-barrier film, high-barrier sheet, high-barrier hollow container, high-barrier tube, high-barrier fuel tank for various purposes, used for packaging all kinds of food, medicine, cigarettes, clothing, arts and crafts, leather goods, manuscript files, chemical Raw materials and intermediates, pesticides, various oils, precision instruments, optical instruments and lenses. To this end, the invention relates to the following:

A polyvinyl alcohol alloy, substantially from about 5^^% to about 94.99wt ^e /. a polyvinyl alcohol homopolymer, from about 75¥1% to about 5% by weight of the polyamide, from 0.01% by weight to about 20% by weight of the thermal decomposition inhibitor and from 0% to about 20% by weight selected from the group consisting of plasticizers, light stabilizers, and / or the composition of conventional additives for antioxidants.

2. The polyvinyl alcohol alloy according to the above paragraph 1, wherein the thermal decomposition inhibitor is selected from the group consisting of aliphatic phosphates, aliphatic phosphites, and mixtures thereof.

3. The polyvinyl alcohol alloy according to the above paragraph 1, wherein the polyvinyl alcohol alloy is substantially from about 51% to about 80% by weight of a polyvinyl alcohol homopolymer, and about 94.9% by weight to about 5% by weight of the polyamide. And from about 0. lwt% to about 15% by weight, preferably from about 2% by weight to about 5% by weight, more preferably about 0.53⁄4^. ~ About 1.5% by weight of the thermal decomposition inhibitor composition, based on the total weight of the polyvinyl alcohol alloy.

4. The polyvinyl alcohol alloy according to the above paragraph 1, wherein the polyvinyl alcohol alloy is substantially from about 25¥1:% to about 75 wt% of a polyvinyl alcohol homopolymer, about 7 (^1:% to about 2! 3 wt% of polyamide and from about 2% to about 5% by weight of a thermal decomposition inhibitor based on the total weight of the polyvinyl alcohol alloy.

5. The polyvinyl alcohol alloy according to the above paragraph 1, wherein the polyvinyl alcohol alloy is substantially from about 35 to about 70% by weight of a polyvinyl alcohol homopolymer, about 63.5 yen 1% to about 5重量%的约约约。 5wt% of the composition of the thermal decomposition inhibitor, based on the total weight of the polyvinyl alcohol alloy.

6. The polyvinyl alcohol alloy according to any one of items 1 to 5 above, wherein the polyvinyl alcohol homopolymer has a degree of hydrolysis of at least about 88%, preferably at least about 95%, more preferably at least about 99%, and the degree of polymerization is It is about 500-2,500, preferably about 1,700-2,000.

7. The polyvinyl alcohol alloy according to any one of the above items 1 to 5, wherein the polyamide is selected from the group consisting of nylon 6, nylon 66, nylon 11, nylon 1010, nylon 12, nylon 46, nylon 69, nylon 610, nylon 612, Nylon 1212, nylon MXD6, nylon TMDT, copolymers and blends of the above nylons having a molecular weight of about 10,000 to 50,000 and a melt flow index (Ml) of about 1 to 200 g 8%, preferably about 15 - 100g/10min.

8. The polyvinyl alcohol alloy according to any one of the above paragraphs 1 to 5, wherein the thermal decomposition inhibitor is selected from the group consisting of: lactam, amino acid and nylon salt, trimethyl phosphate, triethyl phosphate, tributyl phosphate, sub Trimethyl phosphate, triethyl phosphite, tributyl phosphite.

9. The polyvinyl alcohol alloy according to any one of items 1 to 7, wherein the conventional additive is selected from the group consisting of polyhydric alcohols, such as glycerol, sorbitol, pentaerythritol, ethylene oxide, propylene oxide, ethylene glycol. , polyethylene glycol, polypropylene glycol, glycol ether, propylene glycol ether, glyceryl ether, water, diethylene glycol, triethylene glycol, tetraethylene glycol, and mixtures thereof; alcohol amines, such as ethanolamine, diethanolamine, triethanolamine, And mixtures thereof; carboxylic acids and their salts or esters, such as citric acid, acrylic acid, azelaic acid, sebacic acid, dodecanoic acid, isophthalic acid, terephthalic acid, stearate, monostearyl Acid glyceride, dimer acid, tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester, and mixtures thereof; amines such as 1,4-butanediamine, 1 , 6-hexanediamine, 4, 4,-aminocyclohexane, and mixtures thereof; amides such as stearic acid amide, erucamide, oleic acid amide, hydrazine, hydrazine-dimethylacetamide, and mixtures thereof An aromatic phosphate or phosphite such as triphenyl phosphate, triphenyl phosphite, Bisphenol phosphite, tris(nonylphenyl) phosphite, and mixtures thereof.

10. The polyvinyl alcohol alloy according to the above paragraph 9, wherein the polyvinyl alcohol alloy is substantially from about 15 wt% to 84.8% by weight of a polyvinyl alcohol homopolymer, about 55 wt% to 0%. Approximately 15% by weight of the polyamide, from about 0.1% to about 10% by weight of the thermal decomposition inhibitor and from 0.13⁄4^% to about 20wt%. The processing regulator consists of a total weight based on the polyvinyl alcohol alloy.

A method of producing the polyvinyl alcohol alloy according to any one of the above items 1 to 10, the method comprising: mixing the polyvinyl alcohol homopolymer, the polyamide, the thermal decomposition inhibitor, and the conventional additive The blend is thermoplastically processed and granulated.

12. High barrier resin prepared according to the polyvinyl alcohol alloy of any of the above paragraphs 1 to 10.

13. The high barrier article of item 12, wherein the article is selected from the group consisting of a film, a hollow container, a tube, and a sheet. In the following, the invention will be further illustrated by way of non-limiting examples. However, it should be noted that these examples are not to be construed as limiting the invention. detailed description

In the specification and the appended claims, all parts and percentages are based on weight unless otherwise specifically indicated.

Test

Oxygen transmission according to national standards is: GB/T1038 - 2000

Test method for xylene loss and gasoline loss:

The film was first sealed to a 16 cm, 11 cm wide film bag, and then 50 liters of xylene or gasoline was charged to seal the opening. Weigh on the analytical balance and record the weight and time, continue weighing after 24 or 48 hours, the reduction is the amount of xylene or gasoline lost. The polyvinyl alcohol alloy in this embodiment is made of wty. Polyvinyl alcohol (PVA) (purchased from Beijing Organic Chemical Plant, grade 2099, with a nominal polymerization degree of 2,000, a degree of hydrolysis of 99%) and 84.5 wr% of nylon 6 (PA) (purchased from Guangzhou 榕晟Chemical, its nominal molecular weight is 18, 500), 0.5wt ° /. The composition of trimethyl citrate (purchased from Tianjin Reagent III). After the polyvinyl alcohol (PVA) and nylon (PA) and trimethyl phosphate are thoroughly mixed by a mixer, a twin-screw extruder is used (the temperature of each section is 150 ° C, 170 ° C, 180 °). C, 190 ° C, 200 ° C, 210 ° C and 220 ° C) and granulator extrusion granulation, and then fully dried by a dryer to obtain a thermoplastic processing of polyvinyl alcohol alloy, using a single layer of blown film The film was blown to a film thickness of 12 μm (temperatures of sections: 180 ° C, 200 ° C, 220 ° C and 230 Ό, head temperature: 235 ° C). See Table 1 for their physical and mechanical properties. Example 2

In this embodiment, the polyvinyl alcohol alloy is composed of 45 wt% of polyvinyl alcohol (PVA) (purchased from Beijing Organic Chemical Plant, grade 1799, having a nominal degree of polymerization of 1,700, a degree of hydrolysis of 99%) and 53.5 wt% of nylon 610. (PA) (purchased from Guangzhou Hao Chemical, whose nominal molecular weight is 16,500), 1.5% of a mixture of tributyl acid and triethyl phosphite (mixing ratio 1:0.5, purchased from Tianjin Reagent III) Factory) composition. A mixture of polyvinyl alcohol (PVA) and nylon (PA), tributyl phosphate and triethyl phosphite was thoroughly mixed by a mixer, and a twin-screw extruder was used (the temperature of each section was 150 ° C: , 170 ° C:, 180 ° C, 190 ° C, 200 ° C, 210 ° C and 220 ° C) and granulator extrusion granulation, and then fully dried by a dryer to obtain thermoplastically processable polyethylene Alcohol alloy, using a single layer blown film machine to blow a film with a thickness of 12 microns (temperatures of each section: O'C; 190 °C, 220 °C and 220 °C, head temperature: 220 °C). See Table 1 for their physical and mechanical properties. In this embodiment, the polyvinyl alcohol alloy is made up of 70% by weight of polyethylene glycol (PVA) (purchased from Beijing Organic Chemical Plant, grade 2099, with a nominal degree of polymerization of 2,000, a degree of hydrolysis of 99%), 28% by weight. Nylon 6 (PA), nylon 66 (PA) and nylon 610 (PA) mixtures (purchased from Guangzhou Chemical, with a nominal molecular weight of 17,000, a mixing ratio of 1: 1:0.5) and 2% by weight of nylon 66 Salt composition. The polyvinyl alcohol (P), nylon (PA) and nylon 66 salts were thoroughly mixed by a mixer, and a twin-screw extruder was used (the temperature of each section was 150° (170 ° C, 180 ° C, 190 °, 190 °). C, 200 ° C, 210 ° C and 220 ■ C ) and granulator extrusion granulation, and then fully dried by a dryer to obtain a thermoplastically processed polyvinyl alcohol alloy. The thickness is blown by a single layer blown film machine. 12 micron film (temperatures in sections: 180 ° C, 210 ° C, and 220 ° C, head temperature:

220 ° C). See Table 1 for their physical and mechanical properties. Example 4

The polyvinyl alcohol alloy in this example consisted of 73 wt% polyvinyl alcohol (PVA) (available from Beijing Organic Chemical Plant, grade 1799, having a nominal degree of polymerization of 1,700, a degree of hydrolysis of 99%), 25 wt. Nylon 6 (PA) (purchased from Guangzhou Yan Chemical, with a nominal molecular weight of 18,500) and 2 wt% of a mixture of triethyl sulfite and caprolactam (mixing ratio 1: 1). After the mixture of polyvinyl alcohol (PVA), nylon (PA) and triethyl phosphite and caprolactam was thoroughly mixed by a mixer, a twin-screw extruder was used (the temperature of each section was 150 ° C, 170 ° (,, 180 ° C, 190 ° C, 200 ° C, 210 ° C and 220 ° C) and granulator extrusion granulation, and then fully dried by a dryer to obtain a thermoplastic processing of polyvinyl alcohol alloy, using a single layer The film blowing machine blows a film with a thickness of 12 μm (temperatures of 180 ° (210 °C, 210 °C, 215 °C and 220 °C, head temperature: 225 °C). See Table 1 for physical and mechanical properties. Example 5

The polyvinyl alcohol alloy in this embodiment consists of 55 wt% polyvinyl alcohol (P) (purchased from Beijing Organic Chemical Plant, grade 1799, with a nominal degree of polymerization of 1,700, a degree of hydrolysis of 99%), 38% by weight of nylon 6 (PA) (purchased from Guangzhou Hao Chemical, with a nominal molecular weight of 18,500) And 7wt. /. A mixture of glycerol, amino acid, tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester (mixing ratio: 3: 1: 0.1). Mixing polyvinyl alcohol (PVA), nylon (ΡΑ) and glycerol, amino acid, tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester After the machine is fully mixed, use a twin-screw extruder (temperatures of each section: 150 ° C, 170 ° C, 180 ° C, 190 ° C, 200 ° C, 210 ° C and 220 ° C) and granulator squeeze After granulation, and then sufficiently dried by a dryer, a thermoplastically processed polyvinyl alcohol alloy is obtained, and a film having a thickness of 12 μm is blown by a single layer blown film machine (temperature of each section: 175 ° C, 200 r; 215 °C and 230, the head temperature is: 235 °C). See Table 1 for their physical and mechanical properties. Example 6

The polyvinyl alcohol alloy in this example consisted of 85 wt% polyvinyl alcohol (PVA) (available from Beijing Organic Chemical Plant, grade 1799, having a nominal degree of polymerization of 1,700, a degree of hydrolysis of 99%), 4 wt/. Nylon 6 (PA) (purchased from Guangzhou Yan Chemical, with a nominal molecular weight of 18,500) and llwt% of a mixture of triethyl phosphate, glycerol, N,N-dimethylacetamide (mixing ratio) 0.2: 2: 2) Composition. A mixture of polyvinyl alcohol (PVA), nylon (PA) and triethyl phosphate, glycerol, N,N-dimethylacetamide is thoroughly mixed by a mixer, and a twin-screw extruder is used. The temperature is: 150 ° C, 170 ° C, 180 ° C, 190 ° C, 200 ° (, 210 ° C and 220 ° C) and granulator extrusion granulation, and then fully dried by a dryer to obtain a A thermoplastically processable polyvinyl alcohol alloy using a single layer blown film machine to blow a film having a thickness of 12 microns (temperatures of 170 ° C; 190 ° (at 200 ° C and 220 ° C, head temperature) : 220 ° C ) See Table 1 for physical and mechanical properties. Example 7

In this embodiment, the polyvinyl alcohol alloy is made up of 80% by weight of polyvinyl alcohol (PVA) (purchased from Beijing Organic Chemical Factory, grade 1788, with a nominal polymerization degree of 1,700, a degree of hydrolysis of 88%), and 19% by weight of nylon. 6 (PA) (purchased from Guangzhou Hao Chemical, whose nominal molecular weight is 18,500) and 1^« mixture of polyethylene glycol, amino acid, triphenyl phosphite (mixing ratio 1:1: 0.5) . A mixture of polyvinyl alcohol (PVA), nylon (PA), and a mixture of polyethylene glycol, amino acid, and triphenyl phosphite is thoroughly mixed by a mixer, and a twin-screw extruder is used (the temperature of each section is 150 °C, 170 ° C;, 180 ° C, 190 ° C, 200 ° C, 210 ° C and 220 ° C) and granulator extrusion granulation, and then fully dried by a dryer to obtain thermoplastic processing Polyvinyl alcohol alloy, a film with a thickness of 12 microns was blown by a single layer blown film machine (temperatures of 190X, 200 °C, 220 °C and 225 °C, head temperature: 235 °C). See Table 1 for their physical and mechanical properties. Example 8

The polyvinyl alcohol alloy in this embodiment is composed of 65 wt%. Polyvinyl alcohol (PVA) (purchased from Beijing Organic Chemical Plant, grade 1799, with a nominal degree of polymerization of 1,700, degree of hydrolysis

99%), 30wt% nylon 6 (PA) (purchased from Guangzhou Hao Chemical, its nominal molecular weight is 18,500) and 5wt% triethylene glycol, antioxidant 1010, caprolactam, light stabilizer 788 and 壬A mixture of diacids (mixing ratio 3: 0.01: 0.3: 0.1: 1 ). A mixture of polyvinyl alcohol (PVA), nylon (PA) and triethylene glycol, antioxidant 1010, caprolactam, light stabilizer 788 and sebacic acid is thoroughly mixed by a mixer, and a twin-screw extruder is used. The section temperature is: 150 ° C, 170 ° C, 180 ° C, 190 ° C,

200 ° C, 210 Ό and 220 ° C) and granulator extrusion granulation, and then fully dried by a dryer to obtain a thermoplastic processing of polyvinyl alcohol alloy, using a single layer blown film machine to blow a film thickness of 12 microns (The temperature of each section is: 190 ° C, 200 ° C, 220 ° C and 225

°C, the head temperature is: 235 ° C). See Table 1 for their physical and mechanical properties. Comparative example 1:

This comparative example is made up of 83.5wt. /. Polyvinyl alcohol (PVA) (purchased from Beijing Organic Chemical Plant, grade 1799, nominal polymerization degree 1,700, degree of hydrolysis 99%), 4.5 wt% nylon 6 (PA) (purchased from Guangzhou 榕晟Chemical, which has a nominal molecular weight of 18,500) and 12% by weight of a mixture of triphenyl phosphite and triphenyl phosphate (mixing ratio 1:1). A mixture of polyvinyl alcohol (PVA), nylon (PA), triphenyl phosphate and triphenyl phosphate was thoroughly mixed by a mixer, and a twin-screw extruder was used (temperature of each section: 150 ° C, 170) °C, 180 ° C, 190 ° C, 190 ° C and 190 ° C) and granulator extrusion granulation, completely decomposed and carbonized by extrusion, can not be granulated at all. Comparative example 2:

This comparative example is made up of 83.5 wt% polyvinyl alcohol (PVA) (purchased from Beijing Organic Chemical Plant, grade 1788, with a nominal degree of polymerization of 1,700, a degree of hydrolysis of 88%), 4.5 wt% of nylon 610 ( PA) (purchased from Guangzhou Yan Chemical, with a nominal molecular weight of 18,500) and 12% by weight of a mixture of triphenyl phosphite and glycerol (mixing ratio 0.5: 2). A mixture of polyvinyl alcohol (PVA), nylon 610 (PA), triphenyl phosphate and glycerol was thoroughly mixed by a mixer, and a twin-screw extruder was used (temperature of each section: 150 ° C, 170) °C, 180 ° C!, 190 ° C, 190 ° C and 190 ° C) and granulator extrusion granulation, the particle appearance is dark yellow, accompanied by a strong pungent odor, after sufficient drying A single layer blown film machine blows a film having a thickness of 12 μm (temperatures of sections: 170 ° C, 180 ° C, 190 ° C, and 190 Ό, head temperature: 190 ° C). Refer to Table 2 for physical and mechanical data. Comparative example 3:

This comparative example is made up of 85 wt% polyvinyl alcohol (PVA) (purchased from Beijing Organic Chemical Plant, grade 1788, with a nominal degree of polymerization of 1,700, a degree of hydrolysis of 88%), 15 wt% a mixture of triethanolamine and glycerol (mixing ratio: 0.5:1). A mixture of polyvinyl alcohol (PVA), triethanolamine and glycerin is thoroughly mixed by a mixer, and a twin-screw extruder is used (temperatures of each section are: 150" C, 170 ° C; 180 ° C, 190 ° C, 190 ° C and 19 Q ° C) and granulator extrusion granulation, after drying fully, using a single layer blown film machine to blow a film thickness of 12 microns (temperature of each section: 170 ° C, 180 °C;, 185 ° C and 185 ° C, head temperature: 185 ° C. The physical and mechanical data are shown in Table 2. Comparative example:

This comparative example is composed of 55% of ethylene-vinyl alcohol copolymer (EV0H) (manufacturer: 曰本合成化学, its ethylene content: 32%) and 45wt% of nylon 6 (PA) (purchased from Guangzhou 榕晟Chemical, with a nominal molecular weight of 18,500). After the ethylene-vinyl alcohol copolymer (EV0H) and nylon (PA) were thoroughly mixed by a mixer, a twin-screw extruder was used (the temperature of each section was 170 ° C, 170 ° C, 180 ° C, 190). °C, 210 ° C, 230 ° C and 230 ° C) and granulator extrusion granulation, and then fully dried by a dryer, a single layer of film blowing machine to blow a film thickness of 12 microns (the temperature of each section is : 180 ° C, 220 ° C, 230 ° C and 230 ° C, the head temperature is: 230 ° C). See Table 2 for their physical and mechanical properties. Comparative example 5:

Ethylene-vinyl alcohol copolymer (EV0H) (manufacturer: Nippon Synthetic Chemical Co., Ltd., ethylene content: 32%) was blown by a single layer blown film machine with a thickness of 15 μm (temperature of each section: 180 ° C, 220 °C, 230 Ό and 230 ° C, head temperature: 230 ° C). See Table 2 for their physical and mechanical properties. Comparative example 6:

Nylon 6 (PA) (purchased from Guangzhou Hao Chemical, with a nominal molecular weight of 18,500) After the composition is sufficiently dried, it is cast into a 12 micron nylon using an extrusion casting machine (temperatures of 190 ° C; 220 °, 235 ° C and 235 ° C, head temperature: 240 ° C). See Table 2 for physical and mechanical properties of the film.

Table 1

Ex. 1 - 8 represent Examples 1 to 8

2. See the "Testing" section of this application.

Table 2

Note: 1. CE.l - 6 both represent the comparative examples 1 ~ 6.

2. See the "Testing" section of this application.

From the comparison of the above examples with the comparative examples, it is not difficult to see that Comparative Example 1 uses 4.5% nylon and polyvinyl alcohol P having a degree of hydrolysis of 99 and a high content of aromatic phosphates and phosphites. Chemical. By using the data of Table 1 and Comparative Table 1 of other examples, it is not difficult to see that the data of Example 2 of the present invention is better than the ethylene-vinyl alcohol copolymer when the PVA content of the polyvinyl alcohol is only 45%. The EV0H, polyvinyl alcohol content was: 68%), and the data of Examples 3 and 4 showed that the data were much better than the comparative data. Although the present invention has been described in terms of certain embodiments, the present invention is not limited to the specific embodiments or examples disclosed, but is intended to cover all of the subject matter and scope of the invention as defined by the appended claims Improved form.

Claims

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A polyvinyl alcohol alloy substantially comprising from about 5 wt% to about 94.99 wt% of a polyvinyl alcohol homopolymer, from about 753⁄4% to about 5 wt%. The polyamide, 0.011%; % to about 20% by weight of a thermal decomposition inhibitor and 0 to about 20% by weight of a conventional additive selected from the group consisting of plasticizers, light stabilizers and/or antioxidants.

2. The polyvinyl alcohol alloy according to claim 1, wherein the thermal decomposition inhibitor is selected from the group consisting of aliphatic phosphates, aliphatic phosphites, and mixtures thereof.

3. The polyvinyl alcohol alloy according to claim 1, wherein said polyvinyl alcohol alloy is substantially composed of

~ about 5wt ° /. The polyamide, and about 0. lwt% ~ about 15% by weight, preferably about 2wt ° /. The composition of the thermal decomposition inhibitor, based on the total weight of the polyvinyl alcohol alloy, is about 5% by weight, more preferably about 0.5% by weight to about 1.5% by weight.

4. The polyvinyl alcohol alloy according to claim 1, wherein the polyvinyl alcohol alloy is substantially from about 25 wt% to about 75 wt% of a polyvinyl alcohol homopolymer, from about 70 wt% to about 23 wt% of a polyamide, and about 23⁄4% ~ about 52⁄4^% of the thermal decomposition inhibitor composition, based on the total weight of the polyvinyl alcohol alloy.

The polyvinyl alcohol alloy according to claim 1, wherein said polyvinyl alcohol alloy is substantially from about 353⁄4^/. 5重量%的约约约。 5wt% ~ about 1. 5wt% of thermal decomposition inhibitor composition, based on the total weight of the polyvinyl alcohol alloy, about 75% by weight of the polyvinyl alcohol homopolymer, about 63. 5wt% ~ about 29.5wt% polyamide and about 0. 5wt% ~ about 1. 5wt% thermal decomposition inhibitor composition .

6. The polyvinyl alcohol alloy according to claim 1, wherein the polyvinyl alcohol homopolymer has a degree of hydrolysis of at least about 88%, preferably at least about 95%, more preferably at least about 99%, and a degree of polymerization of about 500-2. 500, preferably about 1,700-2, 000.

7. The polyvinyl alcohol alloy according to claim 1, wherein the polyamide is selected from the group consisting of nylon 6, nylon 66, nylon 11, nylon 1010, nylon 12, nylon 46, nylon 69, nylon 610, nylon 612, nylon 1212, nylon MXD6. , nylon TMDT, above Long copolymers and blends thereof having a molecular weight of about 10, 000-50, 000, melt flow index (of Ml) of from about eight Omin 1- 200g, preferably from about 15-100g / 10min _o

The polyvinyl alcohol alloy according to claim 1, wherein the thermal decomposition inhibitor is selected from the group consisting of lactams, amino acids and nylon salts, trimethyl phosphate, triethyl phosphate, tributyl phosphate, and tridecyl strontium ester. , triamteric acid ethyl ester, tributyl succinate.

9. The polyvinyl alcohol alloy according to claim 1, wherein the conventional additive is selected from the group consisting of polyhydric alcohols such as glycerol, sorbitol, pentaerythritol, ethylene oxide, propylene oxide, ethylene glycol, polyethylene glycol , polypropylene glycol, glycol ether, propylene glycol ether, glyceryl ether, water, diethylene glycol, triethylene glycol, tetraethylene glycol, and mixtures thereof; alcohol amines such as ethanolamine, diethanolamine, triethanolamine, and mixtures thereof; An acid and a salt or ester thereof, such as citric acid, acrylic acid, azelaic acid, sebacic acid, dodecanoic acid, isophthalic acid, terephthalic acid, stearate, glyceryl monostearate, Polyacid, tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester, and mixtures thereof; amines such as 1,4-butanediamine, 1,6-hexane Amine, 4,4,-aminocyclohexane, and mixtures thereof; amides, such as stearic acid amide, erucamide, oleic acid amide, hydrazine, hydrazine-dimethylacetamide, and mixtures thereof; aromatic phosphates Or a phosphite such as triphenyl phosphate, triphenyl phosphite, phosphorous acid Bisphenol decyl ester, tris(nonylphenyl) phosphite, and mixtures thereof.

10. The polyvinyl alcohol alloy according to claim 9, wherein the polyvinyl alcohol alloy is substantially from about 15% by weight to about 84.8% by weight of a polyvinyl alcohol homopolymer, about 55 wt%. 0% ~ about 15wt% of the polyamide, about 0. lwt% ~ about 10wt% of the thermal decomposition inhibitor and 0.1% ~ ~ about 20% by weight of the processing regulator, based on the total weight of the polyvinyl alcohol alloy .

11. A method of preparing the polyvinyl alcohol alloy of claim 1, the method comprising: mixing the polyvinyl alcohol homopolymer, a polyamide, a thermal decomposition inhibitor, and the conventional additive, The mixture is thermoplastically processed and granulated.

12. A high barrier article made from a polyvinyl alcohol alloy according to claim 1.

13. The high barrier article according to claim 12, wherein said article is selected from the group consisting of Membranes, hollow containers, tubes and sheets.