CN102361930A - Thermoplastically processable polyvinyl alcohol alloy and preparation method thereof - Google Patents
Thermoplastically processable polyvinyl alcohol alloy and preparation method thereof Download PDFInfo
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- CN102361930A CN102361930A CN2009801577812A CN200980157781A CN102361930A CN 102361930 A CN102361930 A CN 102361930A CN 2009801577812 A CN2009801577812 A CN 2009801577812A CN 200980157781 A CN200980157781 A CN 200980157781A CN 102361930 A CN102361930 A CN 102361930A
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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
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
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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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- 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
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/m224h0.1MPa as measured by differential pressure measurement according to GB/T1038-2000.
Description
Thermoplastically processable polyvinyl alcohol alloys
And methods of making the same the present application claims priority from chinese patent application 200910127984.9 filed 3, 25, 2009, which is incorporated herein by reference in its entirety. 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 modifier, and a method for preparing the same. The polyvinyl alcohol alloy is suitable for being processed into various films, sheets, pipes, hollow containers and the like with high barrier property through thermoplasticity, and the invention also relates to the products prepared from the polyvinyl alcohol alloy. Background
Polyvinyl alcohol is a known polymer having very excellent high barrier properties. However, polyvinyl alcohol homopolymer (PVA) is not suitable for thermoplastic processing due to its melting point higher than the decomposition temperature. In particular, polyvinyl alcohol homopolymers having a degree of hydrolysis of about 99% are completely impossible to thermoplastically process.
To improve the thermoplastic processability of polyvinyl alcohol homopolymers, ethylene -vinyl alcohol copolymers (EV 0H) have been widely used. However, EV0H is very expensive. Meanwhile, due to the introduction of ethylene copolymerization units, the mechanical strength of EV0H is very obviously reduced compared with that of polyvinyl alcohol homopolymer, so that EV0H is not suitable for being used as a high-barrier heat-shrinkable film. It is also important that the barrier properties of EV0H are significantly reduced by the introduction of ethylene copolymerized units, particularly after moisture absorption. Therefore, EV0H is not as satisfactory in many performances.
US4,952,628 discloses a blend of EV0H and a polyamide. US4,950,513 discloses PVA/nylon blends used in admixture with polyolefins. US4, 640, 852, 5, 055, 355, etc. also disclose blends of nylon and EV 0H.
The blends of the above documents all contain olefin units introduced by blending with polyolefins or possessed by EV0H itself. They all significantly affect the barrier properties of the resulting articles and, due to the high viscosity of the blend, they stick to the metal in the screw, die runner in subsequent blown film applications and the like, and thus cause decomposition and carbonization of the raw materials.
U.S. Pat. No. 4,611,019 discloses a melt extrudable composition consisting essentially of a polyvinyl alcohol homopolymer having a degree of hydrolysis greater than 95% and having a viscosity of 2 (4% aqueous solution of TC in the range of 2 to 30 cm), a plasticizer selected from the group consisting of aromatic sulfonamides, polyols, aromatic sulfonates, aromatic phosphates and phosphites, N-dimethylamides of carboxylic acids, alkylene carbonates, alkylpyrrolidones and mixtures thereof in an amount of 7% to 15% by weight of the polyvinyl alcohol homopolymer, and a polyamide selected from the group consisting of nylon 66, nylon 6, nylon 11, nylon 12, nylon 6, 10 copolymer, nylon 6, 12 copolymer and grafted nylon having a molecular weight of 15,000 to 30,000 by weight of the polyvinyl alcohol homopolymer, wherein the polyvinyl alcohol homopolymer has a degree of hydrolysis of greater than 95% and has a viscosity of 2 (4% aqueous solution of TC in the range of 2 to 30 cm) Molecular weight in the poise range.
The melt-extrudable blend disclosed in this document comprises polyvinyl alcohol, a small amount of polyamide and a large amount of plasticizer. It was found experimentally that 0.5 wt./. 4.5 « ^ percent of the mixture of polyamide resin and plasticizer used in this document does not plasticize polyvinyl alcohol with a degree of hydrolysis greater than about 99%, so US4, 611, 019 has to use polyvinyl alcohol with a degree of hydrolysis of around 95% and plasticize this polyvinyl alcohol with a low degree of hydrolysis with a large amount of plasticizer. However, the use of such a large amount of plasticizer and the use of polyvinyl alcohol having a lower degree of hydrolysis cause serious problems. For example, their use can significantly reduce the barrier properties of the material, making it unable to meet high barrier requirements. In addition, the plasticizers limited by US4, 611, 019 are mostly small molecular toxic substances, which limits the application field thereof; meanwhile, these materials tend to generate irritating gases during thermoplastic processing, and cause bubble residues in films and the like, thereby affecting barrier properties.
Accordingly, there remains 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 meeting the requirements of conventional thermoplastic processing. Summary of The Invention
The present inventors have made extensive and intensive studies to solve the above-mentioned problems of the prior art, and have unexpectedly found that by using the following polyvinyl alcohol alloy of the present invention, it is possible to obtain very excellent thermoplastic processability while maintaining high barrier properties and mechanical strength of polyvinyl alcohol.
According to one aspect of the present invention, there is provided a polyvinyl alcohol alloy consisting essentially of about 5 claystax% to about 94.99 wt. /. Based on the total weight of the polyvinyl alcohol alloy, about, H5 wt% of polyamide, 0.01wt% to 20wt% of thermal decomposition inhibitor and 0 to about 20wt% of conventional additives (e.g., plasticizer, light stabilizer and/or antioxidant).
According to another aspect of the present invention, there is provided a method of preparing a polyvinyl alcohol alloy, the method comprising: the polyvinyl alcohol homopolymer, the polyamide, the thermal decomposition inhibitor and the conventional additives (for example, plasticizers, light stabilizers and/or antioxidants) are mixed, the blend is thermoplastically processed and granulated.
According to yet another aspect of the present invention, there is provided a product made from the polyvinyl alcohol alloy, including, but not limited to, high barrier films, hollow containers, tubing, sheets, and the like. Detailed Description
In the following description of the present invention, numerical values in this application are to be considered as modified by the word "about", unless expressly stated otherwise. However, the inventors have tried to take the values of the examples as precisely as possible, although these values inevitably include some errors.
In the present application, specific or preferred embodiments of the invention may be combined, unless explicitly excluded. Each element of the embodiments of the present application is a specific preferred choice of the generic technical features corresponding thereto. The elements of the embodiments, i.e. the specific preferences, may also be combined with other superordinate features, if these superordinate features can be combined with them. These combinations should be considered part of the original disclosure of the present 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 itself. The term "substantially free" means that the impurity level should be less than about lwt%, or completely free. For example, in the present invention, the polyvinyl alcohol homopolymer is substantially free of copolymerized units of ethylene, and the alloy is also substantially free of olefin blending components.
In the present application, the term "high barrier" refers to a physical barrier to air, in particular oxygen. Typically, 4 butterflies have a gas transmission of less than about 20cm in 24 hours as measured by the differential pressure method of GB/T1038-20003/m2.24h-0. lMPa0
According to one aspect of the present invention, there is provided a polyvinyl alcohol alloy consisting essentially of about 5^ to about 94.99 wt% of a polyvinyl alcohol homopolymer, about w H5 wt% of a polyamide, 0.01 wt./. From 20 to 20wt% of a thermal decomposition inhibitor and from 0 to about 20wt% of conventional additives (e.g., plasticizers, light stabilizers, and/or antioxidants) based on the total weight of the polyvinyl alcohol alloy.
In accordance with one embodiment of the present invention, the polyvinyl alcohol alloy consists essentially of about 5 microspheres. From about 80wt% of a polyvinyl alcohol homopolymer, from about 94.91 wt% to about 5wt% of a polyamide, and from about 0 ^ 1^ 15^ 1% to about 15wt% of a thermal decomposition inhibitor, based on the total weight of the polyvinyl alcohol alloy.
According to another preferred embodiment, the polyvinyl alcohol alloy consists essentially of about 251:% to about 75wt% polyvinyl alcohol homopolymer, about 70 ^ to about 23wt% polyamide, and about 2wt% to about 5wt% thermal decomposition inhibitor, based on the total weight of the polyvinyl alcohol alloy.
According to yet another preferred embodiment, the polyvinyl alcohol alloy consists essentially of
35% to about 70% by weight of polyvinyl alcohol homopolymer, about 63.5% to about 29.5% by weight of polyamide, and about 0.5% to about 1.5% by weight of thermal decomposition inhibitor, based on the total weight of polyvinyl alcohol alloy.
In accordance with another embodiment of the present invention, the polyvinyl alcohol alloy is substantially comprised of about 15wt% to about 84.8 wt% polyvinyl alcohol homopolymer, about 55wt% to about 15wt% polyamide, about 0 ^ 1:/° c. To about 10 wt./. 0. < Lambda > 1 >. To about
20 wt. /. Based on the total weight of the polyvinyl alcohol alloy.
The polyvinyl alcohol homopolymers according to the invention can be obtained from polyvinyl acetate by conventional hydrolysis processes, the degree of hydrolysis of which is preferably at least about 88%, more preferably at least about 95%, most preferably at least about 99%. The polyvinyl alcohol homopolymer may have a degree of polymerization of about 500 to 2, 500, preferably about 1,700 to 2, 000. # the polyvinyl alcohol homopolymer of the present invention is substantially free of copolymerized units of an olefin such as ethylene.
Polyamides suitable for use in the present invention, according to preferred embodiments of 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 610, nylon 612, nylon 1212, nylon MXD6, nylon TMDT, copolymers and blends of the above nylons. The nylon may be amorphous nylon, or may be a thermoplastic elastomer of nylon, or a nylon grafted with maleic anhydride, acrylic, or epoxy. The most preferred polyamides are nylon 6, nylon 66 and mixtures thereof. The polyamide may have a molecular weight of about 10,000 to 50,000 and a melt flow index (Ml) of about 1 to 200g/10min, preferably about 15 to 100g/10mino
Thermal decomposition inhibitors suitable for use in the present invention include, but are not limited to: lactam monomers used for forming nylon, such as caprolactam, decanolactam and the like, amino acids, nylon salts, aliphatic phosphoric acid esters and phosphorous acid esters, such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite are preferable, and trimethyl phosphate, triethyl phosphate, trimethyl phosphite and triethyl phosphite are particularly preferable.
In the present invention, the term "conventional additives" refers to additives commonly used in the processing of polyvinyl alcohol homopolymers or copolymers thereof, such as plasticizers, antioxidants, light stabilizers. The present inventors have found that these conventional additives alone do not provide satisfactory thermoplastic processability and air barrier properties without the use of the above heat stabilizers, particularly aliphatic bony acid esters and phosphites.
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, polyethylene glycol, polypropylene glycol, glycol ethers, propylene glycol ethers, glycerol ethers, water, diethylene glycol, triethylene glycol, tetraethylene glycol, and mixtures thereof, alcohol amines such as ethanolamine, diethanolamine, triethanolamine, and mixtures thereof, carboxylic acids and salts or esters thereof such as citric acid, (meth) acrylic acid, dodecanoic acid, azelaic acid, sebacic acid, isophthalic acid, terephthalic acid, stearates, glycerol monostearate, dimer acid, tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester, and mixtures thereof, amines, 1, 4-butanediamine, 1, 6-hexanediamine, 4, -aminocyclohexane, and mixtures thereof, amides such as stearamide, erucamide, oleamide, Ν -dimethylacetamide, and mixtures thereof, aromatic phosphates or phosphites such as triphenylphosphite, bisphenol phosphite, tris (nonylphenyl) phosphite, trisphosphite, nonylphenyl phosphite, and mixtures thereof, according to embodiments of the present invention.
The polyvinyl alcohol alloy of the invention can also contain common light stabilizers as conventional additives, such as one or more of benzophenone, UV-531, UV-242, BP-4, hindered amine, 788, UV-3034, 744; and/or antioxidants, such as hindered phenols: 1010. 3114, 330, 54, and tombstones: 168. 619, 618.
According to the specific embodiment of the present invention, nano inorganic materials, coloring agents, perfumes, antibacterial agents, etc. may also be included as conventional additives according to actual needs.
According to another aspect of the present invention, there is provided a method of preparing a polyvinyl alcohol alloy, the method comprising: the polyvinyl alcohol homopolymer, the polyamide, the thermal decomposition inhibitor and the conventional additives are mixed, and the blend is thermoplastically processed and pelletized. 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, twin-screw extruders with reactive degassing.
According to another aspect of the present invention, there is provided a product made from the polyvinyl alcohol alloy, including, but not limited to, high barrier films, hollow containers, tubing, sheets, and the like. Preferably, the products may include, but are not limited to: single-layer film, multi-layer co-extruded film, high-temperature steaming film, silk-oriented stretched film and heat-shrinkable film; automobile fuel tanks, bottles, barrels; fuel oil or oil delivery pipe, gas delivery pipe.
By comparing the data described in table 2 of the examples, it is not obvious that the products made of the polyvinyl alcohol alloy of the present invention have better tensile strength and elongation at break than the blends of EV0H and EV0H with PA, and have excellent gas barrier property and fragrance retention property. The present inventors have also unexpectedly found that the alloy material has more excellent organic solvent resistance, oil resistance, and chemical resistance than pure polyvinyl alcohol alone or pure polyamide resin alone. The data in Table 1 also show that when the PVA content of the product of the invention is about 45 wt. /. The properties are better than those of the prior art materials, and the properties are more incomparable with those of the prior art materials when the PVA content is about 70wt%, and the materials have very good processability, film forming property 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 film blowing machine, and is continuously extrusion-blown for about 100 hours under processing conditions of temperatures of about 170 ℃, 190 ℃, 210 ℃ and 230 ℃ respectively, without decomposition and carbonization, while having very good transparency.
According to a specific embodiment of the present invention, a five-layer coextrusion apparatus is utilized to form a film having an oxygen transmission of less than about 1.2 cm using the polyvinyl alcohol alloy of the present invention as a barrier layer (5 microns thick) and polyethylene or the like as the other layer (95 microns thick)3/ m224h-0. IMPa, is significantly superior to the same coextruded film with ethylene-vinyl alcohol copolymer (EV 0H) as the barrier layer.
According to the specific embodiment of the invention, the polyvinyl alcohol alloy can be prepared into a multi-layer co-extruded high-resistance heat-insulation shrink film or a two-way stretching film which cannot be performed by ethylene-vinyl alcohol copolymer (EV 0H).
By combining with other classes of materials, such as: the polyvinyl alcohol alloy can be made into various high-barrier films, high-barrier sheets, high-barrier hollow containers, high-barrier pipes and high-barrier oil boxes with different purposes, and can be used for packaging various foods, medicines, cigarettes, clothes, arts and crafts, leather products, manuscript files, chemical raw materials and intermediates, pesticides, various oils, precision instruments, optical instruments, lenses and the like. To this end, the invention relates to the following:
1. a polyvinyl alcohol alloy consisting essentially of from about 5^ about to about 94.99wt ^ aboute/. From about 75% to about 5% by weight of a polyamide, from 0.01% to about 20% by weight of a thermal decomposition inhibitor and from 0 to about 20% by weight of conventional additives selected from plasticizers, light stabilizers and/or antioxidants.
2. The polyvinyl alcohol alloy according to clause 1, wherein the thermal decomposition inhibitor is selected from the group consisting of aliphatic phosphoric acid esters, aliphatic phosphorous acid esters, and mixtures thereof.
3. The polyvinyl alcohol alloy of clause 1, wherein the polyvinyl alcohol alloy consists essentially of from about 51% to about 80% by weight of a polyvinyl alcohol homopolymer, from about 94.9% to about 5% by weight of a polyamide, and from about 0. lwt% to about 15% by weight, preferably from about 2% to about 5% by weight, more preferably about 0.5% of MicroBlock. From about 1.5wt% of a thermal decomposition inhibitor, based on the total weight of the polyvinyl alcohol alloy.
4. The polyvinyl alcohol alloy of clause 1, wherein the polyvinyl alcohol alloy consists essentially of about 25% to about 1:% to about 75% by weight of a polyvinyl alcohol homopolymer, about 7(^1:% to about 2! 3% by weight of a polyamide, and 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 of clause 1, wherein the polyvinyl alcohol alloy consists essentially of about 35 to about 70wt% of a polyvinyl alcohol homopolymer, about 63.5 to about 29.5 wt% of a polyamide, and about 0.5 to about 1.5wt% of a thermal decomposition inhibitor, based on the total weight of the polyvinyl alcohol alloy.
6. The polyvinyl alcohol alloy according to any one of clauses 1 to 5, 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 any one of clauses 1 to 5, wherein the polyamide is selected from 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, has a molecular weight of about 10,000 to 50,000, and a melt flow index (Ml) of about 1 to 200g octaOmin, preferably about 15 to 100g/10 min.
8. The polyvinyl alcohol alloy according to any one of items 1 to 5 above, wherein the thermal decomposition inhibitor is selected from: lactams, amino acids and nylon salts, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite.
9. The polyvinyl alcohol alloy according to any one of the above items 1 to 7, wherein the conventional additive is selected from the group consisting of polyhydric alcohols such as glycerin, sorbitol, pentaerythritol, ethylene oxide, propylene oxide, ethylene glycol, polyethylene glycol, polypropylene glycol, ethylene glycol ethers, propylene glycol ethers, glycerin ethers, water, diethylene glycol, triethylene glycol, tetraethylene glycol, and mixtures thereof, alcohol amines such as ethanolamine, diethanolamine, triethanolamine, and mixtures thereof, carboxylic acids and salts or esters thereof such as citric acid, acrylic acid, azelaic acid, sebacic acid, dodecanoic acid, isophthalic acid, terephthalic acid, stearate, glyceryl monostearate, dimer acid, tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester, and mixtures thereof, amines such as 1, 4-butanediamine, 1, 6-hexanediamine, 4-aminocyclohexane, and mixtures thereof, amides such as stearic acid amide, erucic acid amide, oleic acid amide, Ν -dimethylacetamide, and mixtures thereof, aromatic phosphates or phosphites such as triphenyl phosphate, triphenyl phosphite, bisphenol phosphite, nonyl phosphite, and mixtures thereof.
10. The polyvinyl alcohol alloy of clause 9, wherein the polyvinyl alcohol alloy consists essentially of about 15wt% to ^ 84.8 wt% of a polyvinyl alcohol homopolymer, about 55wt% to about 15wt% of a polyamide, about 0.1 \ ^ 10wt% of a thermal decomposition inhibitor, and 0.1% to about 20 wt.%/. Based on the total weight of the polyvinyl alcohol alloy.
11. A method of making the polyvinyl alcohol alloy of any of clauses 1-10, comprising: mixing said polyvinyl alcohol homopolymer, polyamide, thermal decomposition inhibitor and said conventional additives, thermoplastically processing said blend and pelletizing.
12. High barrier system prepared from polyvinyl alcohol alloy according to any one of the previous clauses 1-10
13. The high barrier article according to clause 12, wherein the article is selected from the group consisting of a film, a hollow container, a tube, and a sheet. The invention is further illustrated by the following non-limiting examples. It should be noted that these examples should not be construed as limiting the invention. Detailed Description
In the present specification and the appended claims, all parts and percentages are by weight unless explicitly stated otherwise.
Testing
The oxygen transmission capacity is according to the national standard: GB/T1038-2000
The method for testing the loss amount of the dimethylbenzene and the loss amount of the gasoline comprises the following steps:
the film was first sealed into a 16cm long, 11cm wide film bag, then 50 ml of xylene or gasoline was charged and the opening was sealed. The weight is weighed on an analytical balance and recorded for the time and weight, and after 24 or 48 hours the weight is continued, the reduced portion of which is the lost amount of toluene or gasoline. The polyvinyl alcohol alloy in this example is wty. The polyvinyl alcohol (PVA) (purchased from Beijing organic chemical plant, trademark 2099, with nominal degree of polymerization of 2,000 and degree of hydrolysis of 99%) and nylon 6 (PA) (purchased from Guangzhou banyan sanden chemical industry, with nominal molecular weight of 18,500) at 84.5 wrt%. trimethyl acid (available from Tianjin reagent III). Fully mixing the polyvinyl alcohol (PVA), nylon (PA) and trimethyl phosphate by a mixer, extruding and granulating by a double-screw extruder (the temperature of each section is 150 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃ and 220 ℃) and a granulator, fully drying by a dryer to obtain the hot-plasticity processable polyvinyl alcohol alloy, and blowing a film with the thickness of 12 microns (the temperature of each section is 180 ℃, 200 ℃, 220 ℃ and 230 Ό, and the temperature of a machine head is 235 ℃) by a single-layer film blowing machine. The physical and mechanical properties are shown in Table 1. Example 2
The polyvinyl alcohol alloy in this example was composed of 45wt% of polyvinyl alcohol (PVA) (purchased from Beijing Organization plant, trade name 1799, nominal degree of polymerization 1,700, degree of hydrolysis 99%) and 53.5wt% of nylon 610 (PA) (purchased from Guangzhou Banyancheng chemical, nominal molecular weight 16, 500), 1.5% of a mixture of tributyl tombstone and triethyl phosphite (mixing ratio 1: 0.5, purchased from Tianjin reagent three works). after fully mixing the polyvinyl alcohol (PVA) and nylon (PA), tributyl phosphate and triethyl phosphite, a double screw extruder (temperature of each section: 150. C:, 170:, 180, 190, 200, 210, 220 ℃ and extrusion granulation was used), after fully drying by a dryer, a thermoplastically processable polyvinyl alcohol alloy was obtained, after fully drying the thermoplastic alloy in a single layer blowing film thickness of 12 micrometers (temperature of each section: O' 190 ℃, 190, 220 ℃, 220:, 150 ℃ and 220:, a single layer blowing temperature of the Polyvinyl Alcohol (PA) and a mixture of nylon 610, 220.2, a mixture of PVA, a polyvinyl alcohol (purchased from Beijing Oriental blowing machine, a mechanical granulator, a temperature of PVA, a mixture of PVA, a mono blowing machine, a temperature of 150, a temperature of PVA, a mono-layer of PA) and a thermoplastic nylon 610, a thermoplastic nylon 6 ℃, a mono-layer of a mixture of nylon 610, a Polypropylene (PA) and a mixture of nylon 6, a polypropylene (purchased from Beijing Oriental nylon) and a mono-layer extrusion granulator, a mono-layer extrusion-layer extrusion-layer extrusion:
220 ℃ C.). The physical and mechanical properties are shown in Table 1. Example 4
The polyvinyl alcohol alloy in this example consisted of 73wt% polyvinyl alcohol (PVA) (purchased from beijing organic chemical plant, designation 1799, with a nominal degree of polymerization of 1,700, and a degree of hydrolysis of 99%), 25 wt./. Nylon 6 (PA) (available from guangzhou sanden chemical with a nominal molecular weight of 18, 500) and 2wt% of a mixture of triethyl phosphite and caprolactam in a mixing ratio of 1: 1. Polyvinyl alcohol (PVA), nylon (PA), a mixture of triethyl phosphite and caprolactam are fully mixed by a mixer, extruded and granulated by a double-screw extruder (the temperature of each section is 150 ℃, 170 ℃ (, 180 ℃, 190 ℃, 200 ℃, 210 ℃ and 220 ℃) and a granulator, and fully dried by a dryer to obtain a thermoplastically processed polyvinyl alcohol alloy, and a film with the thickness of 12 microns is blown by a single-layer film blowing machine (the temperature of each section is 180 ℃ (, 210 ℃, 215 ℃ and 220 ℃, and the temperature of a machine head is 225 ℃), and the physical and mechanical properties of the alloy are shown in Table 1, example 5 and the like
The polyvinyl alcohol alloy in this example was compounded from 55wt% of polyvinyl alcohol (P) (purchased from beijing organization plant, trade name 1799, nominal degree of polymerization 1,700, degree of hydrolysis 99%), 38wt% of nylon 6 (PA) (purchased from guangzhou banyan cheng chemical, nominal molecular weight 18, 500) and 7 wt./. of a mixture of glycerol, amino acids, pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (mixing ratio: 3: 1: 0.1). after mixing polyvinyl alcohol (PVA), nylon (Α) and a mixture of glycerol, amino acids, pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], a twin-screw extruder (temperature of each section: 150 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃) and a thermoplastic film was fully blown through a pelletizer, a hot-blow-dry film was obtained, the melt-blown into a thermoplastic film with a thickness of each section of 175 ℃ and a thickness of each section of a thermoplastic film was molded by a hot-air-blow-dry film machine (temperature of 200 ℃, a temperature of each section: 230 ℃ was measured at a temperature of 175 ℃ and a temperature of a hot-melt-dry film was measured by a hot-dry film machine (temperature of a machine, a temperature of each section of a temperature of 175 ℃ of a temperature of a
The polyvinyl alcohol alloy in this example consisted of 85wt% polyvinyl alcohol (PVA) (purchased from beijing organic chemical plant, designation 1799, with a nominal degree of polymerization of 1,700, and a degree of hydrolysis of 99%), 4 wt/. Nylon 6 (PA) (purchased from Guangzhou Yangshan sanden chemical engineering and having a nominal molecular weight of 18, 500) and a mixture of llwt% triethyl phosphate, glycerol and N, N-dimethylacetamide (the mixing ratio is 0.2: 2: 2). Polyvinyl alcohol (PVA), nylon (PA), triethyl phosphate, glycerol and N, N-dimethylacetamide were thoroughly mixed in a mixer, extruded and pelletized in a twin-screw extruder (temperatures of 150 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃ (210 ℃ and 220 ℃) and a pelletizer, and then thoroughly dried in a dryer to obtain a thermoplastically processable polyvinyl alcohol alloy, and a 12 μm thick film was blown in a single-layer film blowing machine (temperatures of 170 ℃, 190 ℃, 200 ℃ and 220 ℃, head temperature: 220 ℃)
The polyvinyl alcohol alloy in this example consists of 80wt% of polyvinyl alcohol (PVA) (purchased from beijing organic chemical plant, trade mark 1788, with nominal polymerization degree of 1,700 and hydrolysis degree of 88%), 19wt% of nylon 6 (PA) (purchased from guangzhou yansheng chemical industry, with nominal molecular weight of 18, 500) and a mixture of polyethylene glycol, amino acid and triphenyl phosphite of 1^ « (mixing ratio 1:1: 0.5). Fully mixing a mixture of polyvinyl alcohol (PVA), nylon (PA) and a mixture of polyethylene glycol, amino acid and triphenyl phosphite by a mixer, extruding and granulating by a double-screw extruder (the temperature of each section is 150 ℃ and 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃ and 220 ℃) and a granulator, fully drying by a dryer to obtain a thermoplastically-processable polyvinyl alcohol alloy, and blowing a film with the thickness of 12 micrometers (the temperature of each section is 190X, 200 ℃, 220 ℃ and 225 ℃ and the temperature of a machine head is 235 ℃) by a single-layer film blowing machine. The physical and mechanical properties are shown in Table 1. Example 8
The polyvinyl alcohol alloy in this example consists of 65 wt./. Is a polyvinyl alcohol (PVA) (available from Beijing Organization plant, designation 1799, having a nominal degree of polymerization of 1,700 and a degree of hydrolysis of
99 percent of nylon 6 (PA) (which is purchased from Guangzhou banyan sanderian chemical engineering and has the nominal molecular weight of 18 and 500) and 5 percent of triethylene glycol, antioxidant 1010, caprolactam, a mixture of a light stabilizer 788 and azelaic acid (the mixing ratio is 3: 0.01: 0.3: 0.1: 1). Fully mixing a mixture of polyvinyl alcohol (PVA), nylon (PA), triethylene glycol, an antioxidant 1010, caprolactam, a light stabilizer 788 and azelaic acid by a mixer, and then adopting a double-screw extruder (the temperature of each section is 150 ℃, 170 ℃, 180 ℃, 190 ℃, or,
200 ℃, 210 Ό and 220 ℃) and a granulator, and then fully drying the mixture by a dryer to obtain the thermoplastically processable polyvinyl alcohol alloy, and blowing a film with the thickness of 12 microns by a single-layer film blowing machine (the temperature of each section is: 190 ℃, 200 ℃, 220 ℃ and 225
C, the head temperature is: 235 ℃ C.). The physical and mechanical properties are shown in Table 1. Comparative example 1:
this comparative example consisted of 83.5 wt. /. The polyvinyl alcohol (PVA) (purchased from Beijing organic factory, trade name 1799, with nominal polymerization degree of 1,700 and hydrolysis degree of 99%), 4.5wt% of nylon 6 (PA) (purchased from Guangzhou Cheng chemical engineering, with nominal molecular weight of 18, 500) and 12wt% of a mixture of triphenyl phosphite and triphenyl phosphate (mixing ratio 1: 1). Fully mixing polyvinyl alcohol (PVA), nylon (PA), triphenyl phosphate and triphenyl phosphate by a mixer, extruding and granulating by a double-screw extruder (the temperature of each section is 150 ℃, 170 ℃, 180 ℃, 190 ℃ and 190 ℃) and a granulator, and completely decomposing and carbonizing by extrusion, so that granulation cannot be carried out at all. Comparative example 2:
this comparative example consisted of 83.5wt% polyvinyl alcohol (PVA) (purchased from beijing organic chemical plant, trade mark 1788, nominal degree of polymerization of 1,700, degree of hydrolysis 88%), 4.5wt% nylon 610 (PA) (purchased from guangzhou banyan cheng chemical, nominal molecular weight of 18, 500) and 12wt% mixture of triphenyl phosphite and glycerol (mixing ratio 0.5: 2). Polyvinyl alcohol (PVA), nylon 610 (PA), triphenyl phosphate and glycerol are mixed by a mixer, extruded and granulated by a double-screw extruder (the temperature of each section is 150 ℃, 170 ℃, 180 ℃, 190 ℃ and 190 ℃) and a granulator, the appearance of the granules is dark yellow and is accompanied with strong pungent smell, and after full drying, a film with the thickness of 12 microns is blown by a single-layer film blowing machine (the temperature of each section is 170 ℃, 180 ℃, 190 ℃ and 190 Ό, and the temperature of a machine head is 190 ℃). The physical and mechanical data are shown in Table 2. Comparative example 3:
this comparative example consisted of 85wt% polyvinyl alcohol (PVA) (available from Beijing organic chemical industry Co., Ltd., trade name 1788, nominal degree of polymerization of 1,700, degree of hydrolysis 88%), 15wt% of a mixture of triethanolamine and glycerol (mixing ratio: 0.5: 1). Fully mixing a mixture of polyvinyl alcohol (PVA), triethanolamine and glycerol by a mixer, extruding and granulating by a double-screw extruder (the temperature of each section is 150 ℃ and 170 ℃, 180 ℃, 190 ℃ and 19Q ℃) and a granulator, fully drying, and blowing a film with the thickness of 12 microns by a single-layer film blowing machine (the temperature of each section is 170 ℃, 180 ℃, 185 ℃ and 185 ℃, and the head temperature is 185 ℃). The physical and mechanical data are shown in Table 2. Comparative example:
the comparative example consists of 55^ percent of ethylene-vinyl alcohol copolymer (EV 0H) (manufacturer: Ben synthetic chemistry, ethylene content: 32%) and 45wt% of nylon 6 (PA) (purchased from Guangzhou Cheng chemical engineering, nominal molecular weight 18, 500). After the ethylene-vinyl alcohol copolymer (EV 0H) and the nylon (PA) were thoroughly mixed in a mixer, a twin-screw extruder (the temperatures in the respective zones were 170 ℃, 180 ℃, 190 ℃, 210 ℃, 230 ℃ and 230 ℃) and a pelletizer were used to extrude and granulate, and after thoroughly drying in a dryer, a film having a thickness of 12 μm was blown by a single-layer film blower (the temperatures in the respective zones were 180 ℃, 220 ℃, 230 ℃ and 230 ℃, and the head temperature was 230 ℃). The physical and mechanical properties are shown in Table 2. Comparative example 5:
an ethylene-vinyl alcohol copolymer (EV 0H) (manufacturer: Japan synthetic chemistry, ethylene content: 32%) was blown into a film having a thickness of 15 μm (each zone temperature: 180 ℃, 220 ℃, 230 Ό and 230 ℃, head temperature: 230 ℃) using a single layer film blower. The physical and mechanical properties are shown in Table 2. Comparative example 6:
nylon 6 (PA) (purchased from guangzhou sanden chemical with a nominal molecular weight of 18, 500) was fully dried and cast into 12 micron nylon films using an extrusion casting machine (temperature of each section: 190;, 220, 235 and 235 ℃ with a head temperature of 240 ℃), with physical and mechanical properties as shown in table 2.
TABLE 1
Ex.1-8 represent examples 1-8
2. See the "test" section of the present application
TABLE 2
Note: CE.l-6 represent comparative examples 1 to 6.
2. See the "test" section of the present application
As can be seen by comparing the above examples with comparative examples, comparative example 1 using 4.5% nylon and polyvinyl alcohol P having a degree of hydrolysis of 99 and high contents of aromatic phosphoric acid esters and phosphorous acid esters does not plasticize the synthetic material at all. From the data in other examples Table 1 and comparative example Table 1, it can be seen that the data in inventive example 2 are better than those in comparative examples such as ethylene-vinyl alcohol copolymer (EV 0H, polyvinyl alcohol content: 68%) when the polyvinyl alcohol PVA content is only 45%, and the data in examples 3 and 4 are much better than those in comparative examples. While the invention has been described in connection with certain embodiments, the invention is not to be limited to the specific embodiments or examples disclosed, but is intended to cover all modifications that are within the spirit and scope of the invention as defined by the appended claims.
Claims (13)
- Claims to follow1. A polyvinyl alcohol alloy consisting essentially of about 5wt% to about 94.99 wt% of a polyvinyl alcohol homopolymer, about 75wt% to about 5 wt./. From 0.011 to about 20 wt.% of a thermal decomposition inhibitor and from 0 to about 20 wt.% of conventional additives 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 phosphate esters, aliphatic phosphite esters, and mixtures thereof.
- 3. The polyvinyl alcohol alloy according to claim 1, wherein the polyvinyl alcohol alloy consists essentially ofTo about 5 wt./. And about 0. lwt% to about 15% by weight, preferably about 2% by weight. From about 5wt%, more preferably from about 0.5 wt% to about 1.5wt%, of a thermal decomposition inhibitor, based on the total weight of the polyvinyl alcohol alloy.
- 4. The polyvinyl alcohol alloy according to claim 1, wherein the polyvinyl alcohol alloy consists essentially of about 25wt% to about 75wt% of polyvinyl alcohol homopolymer, about 70wt% to about 23wt% of polyamide, and about 2 acr% to about 5 acr% of a thermal decomposition inhibitor, based on the total weight of the polyvinyl alcohol alloy.
- 5. The polyvinyl alcohol alloy of claim 1, wherein the polyvinyl alcohol alloy consists essentially of about 35 particles. From about 70wt% of a polyvinyl alcohol homopolymer, from about 63.5 wt% to about 29.5 wt% of a polyamide, and from about 0.5 wt% to about 1.5wt% of a thermal decomposition inhibitor, based on the total weight of the polyvinyl alcohol alloy.
- 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, copolymers and blends of the foregoing nylons having a molecular weight of from about 10,000 to about 50,000 and a melt flow index (Ml) of from about 1 to about 200g octamin, preferably from about 15 to about 100g/10mino
- 8. 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, tri tombstone acid, triethyl tombstone acid, tributyl tombstone acid.
- 9. The polyvinyl alcohol alloy according to claim 1, wherein said conventional additive is selected from the group consisting of polyols such as glycerol, sorbitol, pentaerythritol, ethylene oxide, propylene oxide, ethylene glycol, polyethylene glycol, polypropylene glycol, ethylene glycol ethers, propylene glycol ethers, glycerol ethers, water, diethylene glycol, triethylene glycol, tetraethylene glycol, and mixtures thereof, alcohol amines such as ethanolamine, diethanolamine, triethanolamine, and mixtures thereof, carboxylic acids and salts or esters thereof such as citric acid, acrylic acid, azelaic acid, sebacic acid, dodecanoic acid, isophthalic acid, terephthalic acid, stearate salts, glycerol monostearate, dimer acid, tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester, and mixtures thereof, amines such as 1, 4-butanediamine, 1, 6-hexanediamine, 4, -aminocyclohexane, and mixtures thereof, amides such as stearamide, erucamide, oleamide, Ν -dimethylacetamide, and mixtures thereof, aromatic phosphates or phosphites such as triphenyl phosphate, triphenyl phosphite, bisphenol Α phosphite, tris (nonylphenyl) phosphite, and mixtures thereof.
- 10. The polyvinyl alcohol alloy of claim 9, wherein the polyvinyl alcohol alloy consists essentially of about 15wt% to about 84.8 wt% of a polyvinyl alcohol homopolymer, about 55wt °/. From 0% to about 15% by weight of a polyamide, from about 0. lwt% to about 10% by weight of a thermal decomposition inhibitor, and from 0.1 \ Lambda% to about 20% by weight of a processing modifier, based on the total weight of the polyvinyl alcohol alloy.
- 11. A method of making the polyvinyl alcohol alloy of claim 1, the method comprising: the polyvinyl alcohol homopolymer, the polyamide, the thermal decomposition inhibitor and the conventional additives are mixed, and the blend is thermoplastically processed and pelletized.
- 12. A high barrier article made from the polyvinyl alcohol alloy according to claim 1.
- 13. The high barrier article according to claim 12, wherein the article is selected from the group consisting of films, hollow containers, tubing, and sheets.
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| CN2009801577812A CN102361930B (en) | 2009-03-25 | 2009-11-02 | Thermoplastically processable polyvinyl alcohol alloy and preparation method thereof |
| PCT/CN2009/001212 WO2010108307A1 (en) | 2009-03-25 | 2009-11-02 | Thermoplastically processable polyvinyl alcohol alloy and preparation method thereof |
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| CN114410042A (en) * | 2022-01-28 | 2022-04-29 | 孙琇芳 | Polyvinyl alcohol/polyamide slow water-soluble food packaging film |
| CN115707734A (en) * | 2021-08-20 | 2023-02-21 | 中国石油化工股份有限公司 | Thermoplastic sulfonic acid group copolymerized polyvinyl alcohol resin with low melting point and high thermal stability as well as preparation method and application thereof |
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| JP6416756B2 (en) * | 2012-06-13 | 2018-10-31 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ | Thermoplastic melt blend composition containing amino acid heat stabilizer |
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| US4611019A (en) * | 1985-06-17 | 1986-09-09 | Lutzmann H Harald | Enhanced barrier compositions from polyvinyl alcohol |
| JP2616221B2 (en) * | 1990-11-09 | 1997-06-04 | 東レ株式会社 | Resin composition |
| FR2731005B1 (en) * | 1994-12-29 | 1997-04-04 | Atochem Elf Sa | POLYAMIDE-BASED POWDER COMPOSITION FOR COATING METALLIC SUBSTRATES |
| US6364987B1 (en) * | 1999-03-10 | 2002-04-02 | Kuraray Co., Ltd. | Method for producing gas barrier film |
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| CN115707734A (en) * | 2021-08-20 | 2023-02-21 | 中国石油化工股份有限公司 | Thermoplastic sulfonic acid group copolymerized polyvinyl alcohol resin with low melting point and high thermal stability as well as preparation method and application thereof |
| CN114410042A (en) * | 2022-01-28 | 2022-04-29 | 孙琇芳 | Polyvinyl alcohol/polyamide slow water-soluble food packaging film |
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