CN105524386B - A kind of thermoplastic modification polyvinyl alcohol resin and preparation method thereof - Google Patents
A kind of thermoplastic modification polyvinyl alcohol resin and preparation method thereof Download PDFInfo
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Abstract
A kind of carboxy-modified medium temperature water-soluble polyvinyl alcohol resin of thermoplasticity, it is made of a effective amount of carboxy-modified polyvinyl alcohol, plasticizer, soft water and processing aid, the carboxy-modified polyvinyl alcohol is obtained through alcoholysis with after the unsaturated monomer copolymerization containing carboxyl by vinyl acetate monomer, 95 (mol) % of its 90.0 (mol) % < alcoholysis degree <, the degree of polymerization are 1000~3500, and carboxyl-content is 0.1~20 mol%；The plasticizer is at least one of glycerine, polyethylene glycol, two tricaprylate of triethylene glycol, and the processing aid is at least one of talcum powder, silica, erucyl amide, saturated aliphatic dicarboxylic acids ester.120-200 DEG C of thermoplasticity carboxy-modified polyvinyl alcohol resin melt temperature obtained, dissolves in 40-60 DEG C of water, 300 DEG C of decomposition temperature or more, water white transparency, non-yellowing, excellent quality.
Description
Technical field
The present invention relates to a kind of modified polyvinylalcohol resins, and in particular to a kind of thermoplasticity carboxy-modified polyvinyl alcohol resin
And preparation method thereof.
Background technology
Polyvinyl alcohol (PVA) is a kind of function admirable, widely used high molecular material, since polyvinyl alcohol has polyhydroxy
The design feature of base, strong hydrogen bonding makes it have many excellent performances, is widely used in coating, adhesive, paper sizing agent
Equal fields.By polyvinyl alcohol resin be used to prepare film or proximate matter be current polyvinyl alcohol resin application new direction, by PVA systems
Standby film or proximate matter has the advantages that excellent resistance oxygen, oil resistance and not static electrification, not dust suction, intensity is high, and in certain item
There is water-soluble and biological degradability, therefore, the film or proximate matter prepared by polyvinyl alcohol is expected to substituting tradition packet under part
Package material prevents to play an important role in terms of white pollution.
But polyvinyl alcohol is crystalline polymer, contains great amount of hydroxy group in molecule, can form a large amount of intramolecular and divide
Hydrogen bond between son makes its fusing point be up to 200-240 DEG C, and decomposition temperature is low, 160 DEG C start dehydration, 200 DEG C start decompose, 220 DEG C
It decomposes completely, the fusing point and decomposition temperature of PVA is close, it is difficult to direct thermoplastic processing molding.
Current technology both domestic and external is to weaken polyvinyl alcohol point by being copolymerized or being added the method for plasticizer blending mostly
With intermolecular Hyarogen-bonding in sub, its fusing point is reduced, thermoplastic processing is made it have, to obtain melt-processable
Modified polyvinylalcohol resin or polyvinyl alcohol blending modified resin.The introducing of relatively large comonomer can effectively reduce polyethylene
Hyarogen-bonding in alcohol molecule, melting temperature and decomposition temperature are clearly separated, and such as EVOH resins, but modifying process is complicated, work
Industry difficulty is big.In existing polyvinyl alcohol production technology, a small amount of modified monomer is introduced in the course of the polymerization process, and melting temperature has
Declined, but still cannot independent thermoplastic processing.
Invention content
Present invention aims at provide a kind of polyvinyl alcohol resin that the carboxy-modified medium temperature of thermoplasticity that quality is good is water-soluble.
Another object of the present invention is to provide the preparation side of the carboxy-modified medium temperature water-soluble polyvinyl alcohol resin of above-mentioned thermoplasticity
Method.
What the object of the invention was achieved through the following technical solutions, it is in parts by weight to be not particularly illustrated below：
A kind of carboxy-modified medium temperature water-soluble polyvinyl alcohol resin of thermoplasticity, it is characterised in that：It is by a effective amount of carboxyl
Modified polyvinylalcohol, plasticizer, soft water and processing aid composition, the carboxy-modified polyvinyl alcohol be by vinyl acetate monomer with
It is obtained through alcoholysis after unsaturated monomer copolymerization containing carboxyl, 90.0 (mol) % < alcoholysis degrees <, 95 (mol) %, the degree of polymerization
It is 1000~3500, carboxyl-content is 0.1~20mol%；The plasticizer is that glycerine, polyethylene glycol, triethylene glycol two are different pungent
At least one of acid esters, the processing aid are in talcum powder, silica, erucyl amide, saturated aliphatic dicarboxylic acids ester
At least one.
The unsaturated monomer containing carboxyl refers to containing more than one COOH group in carboxy-modified polyvinyl alcohol of the present invention
Unsaturated carboxylic acid, esters of unsaturated carboxylic acids or unsaturated acid anhydride, such as itaconic acid, acrylic acid, maleic acid, acrylic acid fourth
Ester, itaconic anhydride, maleic anhydride etc..Above-mentioned saturated aliphatic dicarboxylic acids ester is by containing 2-30 C atom, 1-5 COOH base
The aliphatic acid of group with contain 1-10 C atom, made of the fatty acid of 1-5 OH group, the saturated aliphatic dicarboxylic acids ester
Serial material is commercial product, such as the trade mark of Hangzhou Jin Cheng auxiliary agents Co., Ltd production is the full of G32, G36, G60 etc.
With aliphatic dicarboxylic acid ester.Above-mentioned glycerine, polyethylene glycol, two tricaprylate of triethylene glycol, talcum powder, silica, erucic acid acyl
Amine, saturated aliphatic dicarboxylic acids ester, itaconic acid, acrylic acid, maleic acid, butyl acrylate, itaconic anhydride, maleic anhydride etc.
It is known, commercial product.
Plasticizer of the present invention effectively reduces the melt processing temperature of carboxy-modified PVA；On the one hand soft water of the present invention rises increases
The effect of agent is moulded, swelling action is on the other hand played, PVA molecules is allowed preferably to absorb plasticizer and processing aid.The present invention processes
Auxiliary agent is good with PVA compatibilities.Above-mentioned thermoplasticity carboxy-modified polyvinyl alcohol resin melt temperature is effectively reduced, can be used for melting
Melt thermoplastic processing molding, decomposition temperature is also improved, significantly improves product quality；Meanwhile entire plasticization and modification system profit
Slip is good, and placement is not easy the moisture absorption, adhesion.
In order to further improve the melt-processable of thermoplasticity carboxy-modified polyvinyl alcohol resin of the present invention, improve product
Quality, it is preferable that above-mentioned thermoplasticity carboxy-modified polyvinyl alcohol resin is by 50-85 parts of above-mentioned carboxy-modified polyvinyl alcohols, 5-40
The above-mentioned plasticizer of part, 5-20 parts of above-mentioned soft water and 0.1-15 part above-mentioned processing aids compositions.
Specifically, above-mentioned thermoplasticity carboxy-modified polyvinyl alcohol resin is preferably used by vinyl acetate monomer and itaconic acid
It is obtained through alcoholysis after monomer copolymerization, 90.0 (mol) % < alcoholysis degrees <, 95 (mol) %, the degree of polymerization are 1000~3500, carboxyl
Content is 0.1~20mol%；Above-mentioned plasticizer is mass ratio 2-3：3-4：Glycerine, polyethylene glycol, the triethylene glycol two of 4-6 is different
Caprylate forms, and the processing aid is mass ratio 4-5：0-6：3-5：The talcum powder of 2-4, silica, erucyl amide, saturation
Aliphatic dicarboxylic acid ester forms.
In order to further improve the decomposition temperature of obtained thermoplasticity carboxy-modified polyvinyl alcohol resin, to improve it
Quality, while its weatherability is improved, it is further preferred that a kind of carboxy-modified medium temperature water-soluble polyvinyl alcohol resin of thermoplasticity,
It is characterized in that：It is using a effective amount of carboxy-modified polyvinyl alcohol, plasticizer, soft water, processing aid and crosslinking agent as raw material system
, the carboxy-modified polyvinyl alcohol is obtained through alcoholysis with after the unsaturated monomer copolymerization containing carboxyl by vinyl acetate monomer
, 90.0 (mol) % < alcoholysis degrees <, 95 (mol) %, the degree of polymerization be 1000~3500, carboxyl-content be 0.1~
20mol%；The plasticizer is at least one of glycerine, polyethylene glycol, two tricaprylate of triethylene glycol, the processing aid
For at least one of talcum powder, silica, erucyl amide, saturated aliphatic dicarboxylic acids ester, the crosslinking agent be calcium acetate,
At least one of zinc acetate, copper chloride, zinc chloride, boric acid, borax.
In order to preferably improve the quality of thermoplasticity carboxy-modified polyvinyl alcohol resin, it is highly preferred that above-mentioned thermoplasticity carboxylic
Base modified polyvinylalcohol resin be with 50-85 parts of above-mentioned carboxy-modified polyvinyl alcohols, 5-40 parts of above-mentioned plasticizer, 5-20 parts
Above-mentioned soft water, 0.1-15 parts of above-mentioned processing aids and above-mentioned 0.1-5 parts of crosslinking agent is made for raw material.
Specifically, above-mentioned carboxy-modified polyvinyl alcohol is preferably copolymerized using by vinyl acetate monomer and itaconic anhydride monomer
It is obtained by alcoholysis, 90.0 (mol) % < alcoholysis degrees <, 95 (mol) %, the degree of polymerization are 1000~3500, carboxyl-content is
0.1~20mol%；Above-mentioned plasticizer is mass ratio 2-3：3-4：Glycerine, polyethylene glycol, two tricaprylate of triethylene glycol of 4-6
Composition, above-mentioned processing aid are mass ratio 4-5：0-6：3-5：The talcum powder of 2-4, silica, erucyl amide, representative examples of saturated aliphatic
Dicarboxylic ester forms, and above-mentioned crosslinking agent is mass ratio 3-5：1-2：0-3：1-2：4-6：The calcium acetate of 5-7, zinc acetate, copper chloride,
Zinc chloride, boric acid and borax composition.
Above-mentioned thermoplasticity carboxy-modified polyvinyl alcohol resin can be any shape, such as graininess, cylindrical, cone
Shape, square build, cuboid-type, sheet, disc-shaped, S shapes, V-arrangement, hollow circuit cylinder build, the hollow cone bodily form, hollow square body
At least any shape in type, hollow cuboid-type.
The above-mentioned preferably a diameter of 0.5-15mm of thermoplasticity carboxy-modified polyvinyl alcohol resin, the cylinder of high 0.5-15mm.
The preparation method of above-mentioned thermoplasticity carboxy-modified polyvinyl alcohol resin, prepares according to the following steps：
(1) by 50-85 parts of above-mentioned carboxy-modified polyvinyl alcohols, 5-40 parts of above-mentioned plasticizer, 5-20 parts of soft water, 0.1-
15 parts of above-mentioned processing aids are uniformly mixed and are warming up to 30-90 DEG C, holding 1/6-10 hours；
(2) step (1) described material is delivered in screw extruder, in 120-200 DEG C of temperature, melting extrusion is cooling
To 20-40 DEG C, thermoplasticity carboxy-modified polyvinyl alcohol resin of the present invention is made through pelleter pelletizing moulding.
When containing crosslinking agent in blending constituent described in above-mentioned (1) step, also adds 0.1-5 parts of crosslinking agents and be uniformly mixed.
The hybrid mode of material preferably uses agitating mode to mix in above-mentioned (1) step.
The preferred single screw extrusion machine of screw extruder in above-mentioned (2) step.
Screw extruder is divided into feeding part and screw rod melting extrusion part, wherein feeding part in above-mentioned (2) step
Feeding bin use with blender feeding bin.
Thermoplasticity carboxy-modified polyvinyl alcohol resin of the present invention can be bis- by blowing, extrusion molding, calendering, melting extrusion-
Thermoplasticity carboxy-modified polyvinyl alcohol resin is prepared into film forming or proximate matter to modes such as stretching, melting extrusion-curtain coatings, is further used
In each field packaging, toy, can be also used for preparing 3D printing consumptive material.
Compared with prior art, the present invention having the positive effect that：
1, the melting temperature of thermoplasticity carboxy-modified polyvinyl alcohol resin of the present invention is reduced to 120-200 DEG C, at 40-60 DEG C
Water in dissolve, make thermoplasticity carboxy-modified polyvinyl alcohol resin of the present invention smoothly be used for various thermoplastic processing fields.
2, the decomposition temperature of thermoplasticity carboxy-modified polyvinyl alcohol resin of the present invention be increased to 300 DEG C -350 DEG C, it is colourless
It is bright, non-yellowing；Melt index is 2-8g/10min (150 DEG C/2.16~10kg), and processing fluidity is excellent, good moldability；Crystallization
Degree is (30.0%-60.0%), is used for the excellent in mechanical performance of following process.Using the carboxy-modified polyethylene of thermoplasticity of the present invention
Film or proximate matter intensity prepared by alcohol resin is high, dries rear film or proximate matter intensity reaches 45-120MPa；Resin lubrication is good, no
The moisture absorption, adhesion, while 1 year appearance of placement, color will not change；Non-toxic of the present invention can drop under certain conditions
It solves, be conducive to environmental protection.
The present invention relates to test method it is as follows：
1, the test of melting temperature and decomposition temperature：It is characterized using heat analysis (DSC) curve, crucible used is that high pressure is stainless
Steel crucible is tested in nitrogen atmosphere, heating rate：10 DEG C/min, Range of measuring temp：- 250 DEG C of room temperature.
2, the test of melt index：According to the resin flow behavior of the different PVA trades mark, using fusion index instrument, a constant temperature
Under degree, constant pressure, the mass value that plastic melt flows through standard capillary in 10min, unit g/10min are measured.This test
Method set temperature：140 DEG C~180 DEG C；Pressure：2.16kg~10kg.
3, inflation film stretching strength determination：With reference to standard GB/T 13022-91 stretched plastic film method for testing performances
It is tested.
4, it is molded batten stretching strength determination：It is tested with reference to standard GB/T 1040-79 plastic tensile test methods.
Specific implementation mode
The present invention is specifically described below by embodiment, it is necessary to which indicated herein to be, the present embodiment is served only for
Invention is further explained, should not be understood as limiting the scope of the invention, the person skilled in the art in the field
Some nonessential modifications and adaptations are made to the present invention according to the above, still fall within protection scope of the present invention.Following reality
It applies in example, unless otherwise, all % and number are all as unit of mass percentage, mass weight.
Embodiment 1：By 70 parts of carboxy-modified polyvinyl alcohols, (carboxy-modified polyvinyl alcohol is by vinyl acetate monomer and clothing
Obtained through alcoholysis after the copolymerization of health acid monomers, alcoholysis degree is 92 (mol) %, the degree of polymerization 2200, carboxyl-content 12mol%),
28 parts of two tricaprylates of triethylene glycol, 2 parts of glycerine, 15 parts of soft water, 5 parts of saturated fatty acid race dicarboxylic ester G32,2 parts of erucic acid acyls
Amine is uniformly mixed under stirring, is heated while stirring at a temperature of 44 DEG C, stops heating after 3h.Then band is added in material
Have in the feed bin of stirring, be delivered to material in screw extruder automatically using screw rod, 135 DEG C of extruder temperature is kept, in normal pressure
Under the conditions of melting extrusion, then material is cooled to 25 DEG C, thermoplasticity carboxy-modified polyvinyl alcohol is made through pelleter pelletizing moulding
Resin.
The decomposition temperature of gained thermoplasticity carboxy-modified polyvinyl alcohol resin is 340 DEG C, water white transparency, non-yellowing, melting
125 DEG C of temperature, melt index 6.5g/10min (150 DEG C/2.16~10kg), resin are graininess, water solubility temperature 52-60
℃。
Embodiment 2：By 80 parts of carboxy-modified polyvinyl alcohols, (carboxy-modified polyvinyl alcohol is by vinyl acetate monomer and clothing
Obtained through alcoholysis after health anhydride copolymers, alcoholysis degree be 94 (mol) %, the degree of polymerization 3500, carboxyl-content 17mol%), 10
Part glycerine, 16 parts of polyethylene glycol, 18 parts of soft water, 5 parts of silica, 9 parts of erucyl amides mixing, mix equal under stirring
It is even, it is heated while stirring at a temperature of 90 DEG C, stops heating after 30 minutes.Then material is added in the feed bin with stirring,
Material is delivered in single screw extrusion machine automatically using screw rod, 200 DEG C of extruder temperature is kept, in 0.01MPa (gauge pressure) pressure
Under the conditions of melting extrusion, then material is cooled to 40 DEG C, thermoplasticity carboxy-modified polyvinyl alcohol is made through pelleter pelletizing moulding
Resin.
The decomposition temperature of gained thermoplasticity carboxy-modified polyvinyl alcohol resin is 305 DEG C, and 156 DEG C of melting temperature, melting refers to
Number 3.5g/10min (150 DEG C/2.16~10kg), water solubility temperature are 40-48 DEG C.
Embodiment 3：By 55 parts of carboxy-modified polyvinyl alcohols, (carboxy-modified polyvinyl alcohol is by vinyl acetate monomer and third
It is obtained through alcoholysis after the copolymerization of olefin(e) acid butyl ester, alcoholysis degree is 93 (mol) %, the degree of polymerization 2800, and carboxyl-content is
0.5mol%), 7 parts of two tricaprylates of triethylene glycol, 8 parts of soft water, 0.8 part of silica, 0.2 part of erucyl amide mixing, are being stirred
It is uniformly mixed under state, is heated while stirring at a temperature of 35 DEG C, stop heating after 6h.Then material is added with stirring
In feed bin, material is delivered in single screw extrusion machine automatically using single screw rod, 180 DEG C of extruder temperature is kept, in condition of normal pressure
Lower melting extrusion, then material is cooled to 20 DEG C, thermoplasticity carboxy-modified polyvinyl alcohol resin is made through pelleter pelletizing moulding.
The decomposition temperature of gained thermoplasticity carboxy-modified polyvinyl alcohol resin is 320 DEG C, and 160 DEG C of melting temperature, melting refers to
Number 5g/10min (150 DEG C/2.16~10kg), resin are square shape, and water solubility temperature is 45-55 DEG C.
Embodiment 4：By 63 parts of carboxy-modified polyvinyl alcohols, (carboxy-modified polyvinyl alcohol is by vinyl acetate monomer and third
Olefin(e) acid copolymerization after obtained through alcoholysis, alcoholysis degree be 91 (mol) %, the degree of polymerization 1500, carboxyl-content 6mol%), 22 parts
Mass ratio is 1：1 glycerine and polyethylene glycol, 11 parts of soft water, 5 parts of mass ratioes are 2：3：5 talcum powder, silica and mustard
Sour amide, 5 parts of mass ratioes are 3：1：4 calcium acetate, zinc chloride and boric acid mixing, is uniformly mixed under stirring, at 60 DEG C
At a temperature of heat while stirring, after 2.6 hours stop heating.Then material is added in the feed bin with stirring, using double spiral shells
Material is delivered in single screw extrusion machine by bar automatically, 160 DEG C of extruder temperature of holding, melting extrusion in atmospheric conditions, then will
Material is cooled to 40 DEG C, and thermoplasticity carboxy-modified polyvinyl alcohol resin is made through pelleter pelletizing moulding.
The decomposition temperature of gained thermoplasticity carboxy-modified polyvinyl alcohol resin is 310 DEG C, and 160 DEG C of melting temperature, melting refers to
Number 7g/10min (150 DEG C/2.16~10kg).
Embodiment 5-9：A kind of thermoplasticity carboxy-modified polyvinyl alcohol resin presses following material and technique, remaining same embodiment
4。
The thermoplasticity carboxy-modified polyvinyl alcohol resin obtained by embodiment 5-9,120-200 DEG C of melting temperature, in 40-60
DEG C water in dissolve, decomposition temperature is 300 DEG C -350 DEG C, water white transparency, non-yellowing；Melt index is 2-8g/10min (150
DEG C/2.16~10kg), processing fluidity is excellent, good moldability；Resin crystallization degree is 30.0%-60.0%, is used for following process
Excellent in mechanical performance, the film prepared using thermoplasticity carboxy-modified polyvinyl alcohol resin of the present invention or proximate matter intensity are high, dry
Dry rear film or proximate matter intensity reach 45-120MPa；Thermoplasticity carboxy-modified polyvinyl alcohol resin lubrication is good, it is nonhygroscopic, do not glue
Even, while 1 year appearance of placement, color will not change；Thermoplasticity carboxy-modified polyvinyl alcohol non-toxic of the present invention, can be
It degrades under conditions of certain, be conducive to environmental protection.
Claims (14)
1. a kind of carboxy-modified medium temperature water-soluble polyvinyl alcohol resin of thermoplasticity, it is characterised in that：It is carboxy-modified by 50-85 parts
Polyvinyl alcohol, 5-40 part plasticizer, 5-20 parts of soft water and 0.1-15 parts of processing aid compositions, are in parts by weight, the carboxyl
Modified polyvinylalcohol is obtained through alcoholysis with after the unsaturated monomer copolymerization containing carboxyl by vinyl acetate monomer, 90.0mol%
< alcoholysis degrees < 95mol%, degree of polymerization 1000-3500, carboxyl-content 0.1-20mol%；The plasticizer is glycerine, gathers
At least one of ethylene glycol, two tricaprylate of triethylene glycol, the processing aid are talcum powder, silica, erucyl amide, satisfy
At least one of with aliphatic dicarboxylic acid ester.
2. the carboxy-modified medium temperature water-soluble polyvinyl alcohol resin of thermoplasticity as described in claim 1, it is characterised in that：The saturation
Aliphatic dicarboxylic acid ester is G32, G36 or G60.
3. the carboxy-modified medium temperature water-soluble polyvinyl alcohol resin of thermoplasticity as described in claim 1, it is characterised in that：The carboxyl
Modified polyvinylalcohol is to be obtained through alcoholysis after being copolymerized with itaconic acid monomer by vinyl acetate monomer, 90.0mol% < alcoholysis degrees <
95mol%, degree of polymerization 1000-3500, carboxyl-content 0.1-20mol%；The plasticizer is mass ratio 2-3：3-4：4-6's
Glycerine, polyethylene glycol, two tricaprylate of triethylene glycol composition, the processing aid are mass ratio 4-5：0-6：3-5：The cunning of 2-4
Mountain flour, silica, erucyl amide, saturated aliphatic dicarboxylic acids ester composition.
4. the carboxy-modified medium temperature water-soluble polyvinyl alcohol resin of thermoplasticity as claimed in claim 2, it is characterised in that：The carboxyl
Modified polyvinylalcohol is to be obtained through alcoholysis after being copolymerized with itaconic acid monomer by vinyl acetate monomer, 90.0mol% < alcoholysis degrees <
95mol%, degree of polymerization 1000-3500, carboxyl-content 0.1-20mol%；The plasticizer is mass ratio 2-3：3-4：4-6's
Glycerine, polyethylene glycol, two tricaprylate of triethylene glycol composition, the processing aid are mass ratio 4-5：0-6：3-5：The cunning of 2-4
Mountain flour, silica, erucyl amide, saturated aliphatic dicarboxylic acids ester composition.
5. the carboxy-modified medium temperature water-soluble polyvinyl alcohol resin of thermoplasticity as claimed in claim 2, it is characterised in that：The resin
For cylindrical, a diameter of 0.5-15mm, high 0.5-15mm.
6. a kind of carboxy-modified medium temperature water-soluble polyvinyl alcohol resin of thermoplasticity, it is characterised in that：It is carboxy-modified with 50-85 parts
Polyvinyl alcohol, 5-40 part plasticizer, 5-20 parts of soft water, 0.1-15 parts of processing aids and 0.1-5 parts of crosslinking agents are made for raw material,
In parts by weight, 90.0mol% < alcoholysis degrees < 95mol%, degree of polymerization 1000-3500, carboxyl-content 0.1-20mol%；
The plasticizer is at least one of glycerine, polyethylene glycol, two tricaprylate of triethylene glycol, and the processing aid is talcum
At least one of powder, silica, erucyl amide, saturated aliphatic dicarboxylic acids ester, the crosslinking agent are calcium acetate, acetic acid
At least one of zinc, copper chloride, zinc chloride, boric acid, borax.
7. the carboxy-modified medium temperature water-soluble polyvinyl alcohol resin of thermoplasticity as claimed in claim 6, it is characterised in that：The saturated fat
Fat race dicarboxylic ester is G32, G36 or G60.
8. the carboxy-modified medium temperature water-soluble polyvinyl alcohol resin of thermoplasticity as claimed in claim 6, it is characterised in that：The carboxyl
Modified polyvinylalcohol is to be obtained through alcoholysis after being copolymerized with itaconic anhydride monomer by vinyl acetate monomer, 90.0mol% < alcoholysis degrees
< 95mol%, degree of polymerization 1000-3500, carboxyl-content 0.1-20mol%；The plasticizer is mass ratio 2-3：3-4：4-6
Glycerine, polyethylene glycol, two tricaprylate of triethylene glycol composition, the processing aid be mass ratio 4-5：0-6：3-5：2-4's
Talcum powder, silica, erucyl amide, saturated aliphatic dicarboxylic acids ester composition, the crosslinking agent are mass ratio 3-5：1-2：0-
3：1-2：4-6：Calcium acetate, zinc acetate, copper chloride, zinc chloride, boric acid, the borax of 5-7.
9. the carboxy-modified medium temperature water-soluble polyvinyl alcohol resin of thermoplasticity as claimed in claim 7, it is characterised in that：The carboxyl
Modified polyvinylalcohol is to be obtained through alcoholysis after being copolymerized with itaconic anhydride monomer by vinyl acetate monomer, 90.0mol% < alcoholysis degrees
< 95mol%, the degree of polymerization be 1000~3500, carboxyl-content 0.1-20mol%；The plasticizer is mass ratio 2-3：3-4：4-
6 glycerine, polyethylene glycol, two tricaprylate of triethylene glycol composition, the processing aid are mass ratio 4-5：0-6：3-5：2-4's
Talcum powder, silica, erucyl amide, saturated aliphatic dicarboxylic acids ester composition, the crosslinking agent are mass ratio 3-5：1-2：0-
3：1-2：4-6：Calcium acetate, zinc acetate, copper chloride, zinc chloride, boric acid, the borax of 5-7.
10. the carboxy-modified medium temperature water-soluble polyvinyl alcohol resin of thermoplasticity as claimed in claim 9, it is characterised in that：The tree
Fat is cylindrical, a diameter of 0.5-15mm, high 0.5-15mm cylinder.
11. the preparation method of the carboxy-modified medium temperature water-soluble polyvinyl alcohol resin of the thermoplasticity as described in claim any one of 1-5,
It is characterized in that, prepares according to the following steps：
（1）The carboxy-modified polyvinyl alcohol, plasticizer, soft water, processing aid are uniformly mixed and are warming up to 30-90 DEG C,
It is kept for 1/6-10 hours；
（2）By step（1）Resulting material is delivered in screw extruder, in 120-200 DEG C of melting extrusion, is cooled to 20-40 DEG C,
The carboxy-modified medium temperature water-soluble polyvinyl alcohol resin of thermoplasticity is made through pelleter pelletizing moulding.
12. the preparation method of the carboxy-modified medium temperature water-soluble polyvinyl alcohol resin of thermoplasticity as claimed in claim 11, feature exist
In：The step（1）Middle hybrid mode uses and is stirred mode；The step（2）Middle screw extruder is squeezed using single screw rod
Go out machine；The single screw extrusion machine includes feeding part and screw rod melting extrusion part, and the wherein feeding bin of feeding part uses
Feeding bin with blender.
13. the preparation method of the carboxy-modified medium temperature water-soluble polyvinyl alcohol resin of the thermoplasticity as described in claim any one of 7-10,
It is characterized in that, preparing according to the following steps：
（1）The carboxy-modified polyvinyl alcohol, plasticizer, soft water, processing aid, crosslinking agent are uniformly mixed and are warming up to
It 30-90 DEG C, is kept for 1/6-10 hours；
（2）By step（1）Resulting material is delivered in screw extruder, in 120-200 DEG C of melting extrusion, is cooled to 20-40 DEG C,
The carboxy-modified medium temperature water-soluble polyvinyl alcohol resin of thermoplasticity is made through pelleter pelletizing moulding.
14. the preparation method of the carboxy-modified medium temperature water-soluble polyvinyl alcohol resin of thermoplasticity as claimed in claim 13, feature exist
In：The step（1）Middle hybrid mode uses and is stirred mode；The step（2）Middle screw extruder is squeezed using single screw rod
Go out machine；The single screw extrusion machine includes feeding part and screw rod melting extrusion part, and the wherein feeding bin of feeding part uses
Feeding bin with blender.
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| CN107936430A (en) * | 2016-10-13 | 2018-04-20 | 中国石油化工股份有限公司 | High fluidity polyvinyl alcohol that thermoplastification is modified, cast film materials and preparation method thereof |
| CN111100316B (en) * | 2018-10-25 | 2022-11-11 | 中国石油化工股份有限公司 | Hollow polyvinyl alcohol particles and preparation method thereof |
| 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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| CN101203551A (en) * | 2005-06-16 | 2008-06-18 | 日本合成化学工业株式会社 | Water-solubility membrane |
| CN102391598A (en) * | 2011-09-07 | 2012-03-28 | 北京工商大学 | Polyvinyl alcohol material and production method thereof |
| CN102731710A (en) * | 2011-04-07 | 2012-10-17 | 中国石油化工集团公司 | Carboxyl modified polyvinyl alcohol and method for preparing same |
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2014
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101203551A (en) * | 2005-06-16 | 2008-06-18 | 日本合成化学工业株式会社 | Water-solubility membrane |
| CN102731710A (en) * | 2011-04-07 | 2012-10-17 | 中国石油化工集团公司 | Carboxyl modified polyvinyl alcohol and method for preparing same |
| CN102391598A (en) * | 2011-09-07 | 2012-03-28 | 北京工商大学 | Polyvinyl alcohol material and production method thereof |
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