CN108084320A - A kind of modified polyvinylalcohol and its preparation process - Google Patents
A kind of modified polyvinylalcohol and its preparation process Download PDFInfo
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- CN108084320A CN108084320A CN201711429523.8A CN201711429523A CN108084320A CN 108084320 A CN108084320 A CN 108084320A CN 201711429523 A CN201711429523 A CN 201711429523A CN 108084320 A CN108084320 A CN 108084320A
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- modified polyvinylalcohol
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- vinyl acetate
- methanol solution
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—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 acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
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- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a kind of modified polyvinylalcohol and its preparation process, including more 11 14 parts of acrylate monomers, 91 98 parts of Vinyl Acetate Monomer, 0.6 1 parts of initiator, 700 900 parts of solvent, 150 200 parts of the methanol solution of sodium hydroxide.It concretely comprises the following steps：It adds in whole more acrylate monomers and 30% Vinyl Acetate Monomer in a solvent, is added dropwise initiator, reaction, which started remaining Vinyl Acetate Monomer is added dropwise after five minutes, obtains hyperbranched polyvinyl acetate；It is stirred again, the methanol solution for adding in sodium hydroxide carries out alcoholysis reaction；Finally solidliquid mixture is centrifuged, dry, is crushed, you can obtains modified polyvinylalcohol.For the present invention using more acrylate monomers as raw material, methanol is solvent, and using environmentally friendly solvent in reaction, and obtained modified polyvinylalcohol melting temperature is reduced to 150 DEG C or so, improves the performance of polyvinyl alcohol in various applications.
Description
Technical field
The invention belongs to technical field of polymer materials, more particularly to a kind of modified polyvinylalcohol and its preparation process.
Background technology
Polyvinyl alcohol (Polyviny Alcohol, PVA) appearance is white powder, is that a kind of purposes is quite extensive water-soluble
Property high molecular polymer, performance can be divided into two big purposes of fiber and non-fiber between plastics and rubber.Since PVA has
Unique strong adherence, flexibility, solvent resistance, wearability and specially treated water resistance having, therefore except making
Outside fibrous raw material, the products such as production coating, adhesive, paper product processing agent, emulsifier, dispersant, film are also largely used to, it should
With scope throughout industries such as weaving, food, medicine, building, timber processing, papermaking, printing, agricultural, steel, macromolecule chemical industries.
However, PVA is crystalline polymer, great amount of hydroxy group is contained on main chain, intermolecular and intramolecular forms a large amount of hydrogen bonds,
Causing its melting temperature, fusing point is up to 200 DEG C or more close to decomposition temperature, this produces bigger effect the performance of PVA.Application number
A kind of thin polymer film and its preparation process containing ionic liquid are disclosed for 200610105400.4 patent, by ionic liquid
Body is dissolved into formation uniform solution in the aqueous solution of polyvinyl alcohol and then adds in crosslinking agent, finally obtains the thin of better heat stability
Film however, the ionic liquid used in this patent is expensive, does not illustrate the specific advantage of thermal stability yet.Therefore, it is existing
Polyvinyl alcohol still has the defects of fusing point is high, modified of high cost.
The content of the invention
To solve existing polyvinyl alcohol there are fusing point height, modified deficiency of high cost, the present invention provides a kind of
Modified polyvinylalcohol and its preparation process, to reduce the fusing point of polyvinyl alcohol and improve its heat decomposition temperature.
In order to solve the above technical problems, the present invention provides following technical solutions：
A kind of modified polyvinylalcohol, including following material composition:More acrylate monomer 11-14 parts, vinylacetate list
91-98 parts of body, 0.6-1 parts of initiator, 700-900 parts of solvent, 150-200 parts of the methanol solution of sodium hydroxide.
Further, more acrylate monomers are high propoxylated glycerol triacrylate, three hydroxyl of highly ethoxylatedization
Any one in propane tri, trimethylolpropane tetra-acrylate.
Further, the initiator is any one in azodiisobutyronitrile, azobisisoheptonitrile, dicumyl peroxide
Kind.
Further, the solvent is methanol.
A kind of modified polyvinylalcohol of the present invention has the beneficial effect that：Raw material is simple and easy to get, required at low cost；Made using methanol
For solvent, environmental pollution is alleviated；Melting temperature is reduced to 150 DEG C or so, improves the performance of polyvinyl alcohol product.
A kind of preparation process of modified polyvinylalcohol, comprises the following steps that：
Step 1：11-14 parts of more acrylate monomers and 30% Vinyl Acetate Monomer are added in a solvent,
71-84 DEG C is warming up to, initiator is added dropwise, reaction starts that remaining Vinyl Acetate Monomer is added dropwise after five minutes until dripping
Into, then keep the temperature 1 it is small when start to cool down, obtain hyperbranched polyvinyl acetate；
Step 2：The hyperbranched polyvinyl acetate that step 1 is obtained is stirred, and stirring adds in 50% when starting
Sodium hydroxide methanol solution carry out alcoholysis reaction, under conditions of 55 DEG C react a hour, add in remaining hydroxide
The methanol solution of sodium, the reaction was continued a hour, obtains the solidliquid mixture of modified polyvinylalcohol；
Step 3：The solidliquid mixture for the modified polyvinylalcohol that step 2 is obtained centrifuges, is dry, crushing, you can
Obtain modified polyvinylalcohol.
Further, the degree of polymerization of the modified polyvinylalcohol be 300-4000, alcoholysis degree>70%.
Further, in the step 1, more acrylate monomers are high propoxylated glycerol triacrylate, height
Any one in ethoxylated trimethylolpropane triacrylate, trimethylolpropane tetra-acrylate.
Further, in the step 2, the mass concentration of the methanol solution of the sodium hydroxide is 5%.
The preparation process's of the modified polyvinylalcohol of the present invention has the beneficial effect that：Raw material is simple and easy to get, required at low cost；It adopts
By the use of methanol as solvent, environmental pollution is alleviated；Substep alcoholysis is carried out in alcoholysis, protects the branching characteristics and alcohol of polymer
It is 3 times faster than conventional polyvinyl alcohol to solve speed；Melting temperature is reduced to 150 DEG C or so, and solution viscosity is low, improves polyvinyl alcohol
The performance of product.
Specific embodiment
The specific embodiment of the present invention is described in detail with reference to embodiment, following embodiment is used to illustrate this hair
It is bright, but it is not limited to the scope of the present invention.
Embodiment 1
A kind of modified polyvinylalcohol, including following material composition:More 11 parts of acrylate monomers, Vinyl Acetate Monomer 91
Part, 0.6 part of initiator, 700 parts of methanol solvate, 150 parts of the methanol solution of sodium hydroxide.
Further, the initiator is any one in azodiisobutyronitrile, azobisisoheptonitrile, dicumyl peroxide
Kind.
The preparation process of modified polyvinylalcohol：
Step 1：Whole more acrylate monomers and 30% Vinyl Acetate Monomer are added in methyl alcohol, are heated up
To 71 DEG C, initiator solution is added dropwise, reaction starts that remaining Vinyl Acetate Monomer is added dropwise until being added dropwise to complete, so after five minutes
Start to cool down when heat preservation 1 is small afterwards, obtain hyperbranched polyvinyl acetate；
Step 2：The hyperbranched polyvinyl acetate that step 1 is obtained is stirred, and 75 parts are added in when stirring starts
Mass concentration be 5.6% sodium hydroxide methanol solution carry out alcoholysis reaction, under conditions of 55 DEG C react a hour,
The methanol solution of remaining sodium hydroxide is added in, the reaction was continued a hour, obtains the solidliquid mixture of modified polyvinylalcohol；
Step 3：The solidliquid mixture for the modified polyvinylalcohol that step 2 is obtained centrifuges, is dry, crushing, you can
Obtain modified polyvinylalcohol.
Further, the degree of polymerization of the modified polyvinylalcohol be 300-4000, alcoholysis degree>70%.
Further, in the step 1, more acrylate monomers are high propoxylated glycerol triacrylate, height
Any one in ethoxylated trimethylolpropane triacrylate, trimethylolpropane tetra-acrylate.
The embodiment of the present invention 1 has the beneficial effect that：Raw material is simple and easy to get, required at low cost；Using methanol as solvent, subtract
Light environmental pollution；Substep alcoholysis is carried out in alcoholysis, protect polymer branching characteristics and alcoholysis speed than conventional poly- second
Fast 3 times of enol；Melting temperature is reduced to 151 DEG C, and solution viscosity is low, improves the performance of polyvinyl alcohol product.
Embodiment 2
A kind of modified polyvinylalcohol, including following material composition:More 13 parts of acrylate monomers, Vinyl Acetate Monomer 95
Part, 0.7 part of initiator, 850 parts of methanol solvate, 175 parts of the methanol solution of sodium hydroxide.
Further, the initiator is any one in azodiisobutyronitrile, azobisisoheptonitrile, dicumyl peroxide
Kind.
The preparation process of modified polyvinylalcohol：
Step 1：Whole more acrylate monomers and 30% Vinyl Acetate Monomer are added in methyl alcohol, are heated up
To 78 DEG C, initiator solution is added dropwise, reaction starts that remaining Vinyl Acetate Monomer is added dropwise until being added dropwise to complete, so after five minutes
Start to cool down when heat preservation 1 is small afterwards, obtain hyperbranched polyvinyl acetate；
Step 2：The hyperbranched polyvinyl acetate that step 1 is obtained is stirred, and 80 parts are added in when stirring starts
Mass concentration be 5.6% sodium hydroxide methanol solution carry out alcoholysis reaction, under conditions of 55 DEG C react a hour,
The methanol solution of remaining sodium hydroxide is added in, the reaction was continued a hour, obtains the solidliquid mixture of modified polyvinylalcohol；
Step 3：The solidliquid mixture for the modified polyvinylalcohol that step 2 is obtained centrifuges, is dry, crushing, you can
Obtain modified polyvinylalcohol.
Further, the degree of polymerization of the modified polyvinylalcohol be 300-4000, alcoholysis degree>70%.
Further, in the step 1, more acrylate monomers are high propoxylated glycerol triacrylate, height
Any one in ethoxylated trimethylolpropane triacrylate, trimethylolpropane tetra-acrylate.
The embodiment of the present invention 2 has the beneficial effect that：Raw material is simple and easy to get, required at low cost；Using methanol as solvent, subtract
Light environmental pollution；Substep alcoholysis is carried out in alcoholysis, protect polymer branching characteristics and alcoholysis speed than conventional poly- second
Fast 3 times of enol；Melting temperature is reduced to 153 DEG C, and solution viscosity is low, improves the performance of polyvinyl alcohol product.
Embodiment 3
A kind of modified polyvinylalcohol, including following material composition:More 14 parts of acrylate monomers, Vinyl Acetate Monomer 98
Part, 1 part of initiator, 900 parts of methanol solvate, 200 parts of the methanol solution of sodium hydroxide.
Further, the initiator is any one in azodiisobutyronitrile, azobisisoheptonitrile, dicumyl peroxide
Kind.
The preparation process of modified polyvinylalcohol：
Step 1：Whole more acrylate monomers and 30% Vinyl Acetate Monomer are added in methyl alcohol, are heated up
To 84 DEG C, initiator solution is added dropwise, reaction starts that remaining Vinyl Acetate Monomer is added dropwise until being added dropwise to complete, so after five minutes
Start to cool down when heat preservation 1 is small at 84 DEG C afterwards, obtain hyperbranched polyvinyl acetate；
Step 2：The hyperbranched polyvinyl acetate that step 1 is obtained is stirred, and 100 parts are added in when stirring starts
Mass concentration be 5.6% sodium hydroxide methanol solution carry out alcoholysis reaction, under conditions of 55 DEG C react a hour,
The methanol solution of remaining sodium hydroxide is added in, the reaction was continued a hour, obtains the solidliquid mixture of modified polyvinylalcohol；
Step 3：The solidliquid mixture for the modified polyvinylalcohol that step 2 is obtained centrifuges, is dry, crushing, you can
Obtain modified polyvinylalcohol.
Further, the degree of polymerization of the modified polyvinylalcohol be 300-4000, alcoholysis degree>70%.
Further, in the step 1, more acrylate monomers are high propoxylated glycerol triacrylate, height
Any one in ethoxylated trimethylolpropane triacrylate, trimethylolpropane tetra-acrylate.
The embodiment of the present invention 3 has the beneficial effect that：Raw material is simple and easy to get, required at low cost；Using methanol as solvent, subtract
Light environmental pollution；Substep alcoholysis is carried out in alcoholysis, protect polymer branching characteristics and alcoholysis speed than conventional poly- second
Fast 3 times of enol；Melting temperature is reduced to 149 DEG C, and solution viscosity is low, improves the performance of polyvinyl alcohol product.
The above is the preferred embodiment of the present invention, is not restricted to the present invention.It will be understood by those skilled in the art that
Several improvement and modification made without departing from the principle of the present invention, also should be regarded as protection scope of the present invention.
Claims (7)
1. a kind of modified polyvinylalcohol, which is characterized in that including following material composition:More acrylate monomer 11-14 parts, acetic acid
91-98 parts of vinyl acetate monomer, 0.6-1 parts of initiator, 700-900 parts of solvent, 150-200 parts of the methanol solution of sodium hydroxide.
2. a kind of modified polyvinylalcohol according to claim 1, which is characterized in that more acrylate monomers are high by third
Oxygroup glycerol tri-acrylate, highly ethoxylatedization trimethylolpropane trimethacrylate, trimethylolpropane tetra-acrylate
In any one.
3. a kind of modified polyvinylalcohol according to claim 1, which is characterized in that the initiator is two isobutyl of azo
Any one in nitrile, azobisisoheptonitrile, dicumyl peroxide.
4. a kind of modified polyvinylalcohol according to claim 1, which is characterized in that the solvent is methanol.
5. a kind of preparation process of modified polyvinylalcohol described in claim 1, which is characterized in that comprise the following steps that：
Step 1：11-14 parts of more acrylate monomers and 30% Vinyl Acetate Monomer, heating are added in a solvent
To 71-84 DEG C, initiator is added dropwise, reaction starts that remaining Vinyl Acetate Monomer is added dropwise until being added dropwise to complete, so after five minutes
Start to cool down when heat preservation 1 is small afterwards, obtain hyperbranched polyvinyl acetate；
Step 2：The hyperbranched polyvinyl acetate that step 1 is obtained is stirred, and 50% hydrogen is added in when stirring starts
The methanol solution of sodium oxide molybdena carries out alcoholysis reaction, and a hour is reacted under conditions of 55 DEG C, adds in remaining sodium hydroxide
Methanol solution, the reaction was continued a hour, obtains the solidliquid mixture of modified polyvinylalcohol；
Step 3：The solidliquid mixture for the modified polyvinylalcohol that step 2 is obtained centrifuges, is dry, crushing, you can obtains
Modified polyvinylalcohol.
6. the preparation process of modified polyvinylalcohol according to claim 5, which is characterized in that more acrylate monomers
For high propoxylated glycerol triacrylate, highly ethoxylatedization trimethylolpropane trimethacrylate, trimethylolpropane 4 third
Any one in olefin(e) acid ester.
7. the preparation process of modified polyvinylalcohol according to claim 5, which is characterized in that described in the step 2
The mass concentration of the methanol solution of sodium hydroxide is 5.6%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711429523.8A CN108084320A (en) | 2017-12-26 | 2017-12-26 | A kind of modified polyvinylalcohol and its preparation process |
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| CN201711429523.8A CN108084320A (en) | 2017-12-26 | 2017-12-26 | A kind of modified polyvinylalcohol and its preparation process |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109181184A (en) * | 2018-08-28 | 2019-01-11 | 广州和诚新材料科技有限公司 | A kind of food-grade polyethylene alcohol water soluble film and its preparation process |
| CN109294138A (en) * | 2018-08-28 | 2019-02-01 | 广州和诚新材料科技有限公司 | A kind of food-grade polyethylene alcohol water soluble film and preparation method thereof |
| CN112574342A (en) * | 2020-12-16 | 2021-03-30 | 湖北魔洗高新材料制品有限公司 | Preparation method of polyvinyl alcohol raw material for PVA collodion cotton head production |
| CN114773502A (en) * | 2022-05-07 | 2022-07-22 | 安徽皖维高新材料股份有限公司 | Alcoholysis method of polyvinyl acetate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106854255A (en) * | 2015-12-08 | 2017-06-16 | 中国石化集团四川维尼纶厂 | A kind of modified polyvinylalcohol and preparation method thereof |
-
2017
- 2017-12-26 CN CN201711429523.8A patent/CN108084320A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106854255A (en) * | 2015-12-08 | 2017-06-16 | 中国石化集团四川维尼纶厂 | A kind of modified polyvinylalcohol and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109181184A (en) * | 2018-08-28 | 2019-01-11 | 广州和诚新材料科技有限公司 | A kind of food-grade polyethylene alcohol water soluble film and its preparation process |
| CN109294138A (en) * | 2018-08-28 | 2019-02-01 | 广州和诚新材料科技有限公司 | A kind of food-grade polyethylene alcohol water soluble film and preparation method thereof |
| CN112574342A (en) * | 2020-12-16 | 2021-03-30 | 湖北魔洗高新材料制品有限公司 | Preparation method of polyvinyl alcohol raw material for PVA collodion cotton head production |
| CN114773502A (en) * | 2022-05-07 | 2022-07-22 | 安徽皖维高新材料股份有限公司 | Alcoholysis method of polyvinyl acetate |
| CN114773502B (en) * | 2022-05-07 | 2024-02-09 | 安徽皖维高新材料股份有限公司 | Alcoholysis method of polyvinyl acetate |
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Application publication date: 20180529 |