CN100408604C - Production process of vinylidene chloride resin - Google Patents
Production process of vinylidene chloride resin Download PDFInfo
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- CN100408604C CN100408604C CNB021410054A CN02141005A CN100408604C CN 100408604 C CN100408604 C CN 100408604C CN B021410054 A CNB021410054 A CN B021410054A CN 02141005 A CN02141005 A CN 02141005A CN 100408604 C CN100408604 C CN 100408604C
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- vinylidene chloride
- chloride resin
- vinylidene
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Abstract
The present invention provides a method for producing a vinylidene chloride-based resin, scarcely forming odd-shaped particles. This method for producing the vinylidene chloride-based resin comprises subjecting vinylidene chloride to suspension polymerization, wherein such a methyl cellulose that contains a 1,2-dichloroethane-soluble component in an amount of 0.1-2.0 wt.% is used as a suspending agent for the suspension polymerization.
Description
Technical field
When the present invention relates to use methylcellulose gum to carry out suspension polymerization as suspension agent, the irregular particle of generation is few, can make the manufacture method of the vinylidene chloride resin of uniform single spherolite.
Background technology
In the past, vinylidene chloride resin is because barrier properties for gases, water vapour barrier, the transparency are excellent, and can pass through microwave oven cooking, so be widely used as the shrink-wrap material of food.
These vinylidene chloride resins, generally be to make by the suspension polymerization that the butyrous vinylidene is dispersed in the aqueous medium, when this suspension polymerization, as suspension agent, use the various suspension agents such as partly-hydrolysed thing of derivatived cellulose, polyvinyl alcohol and polyvinyl acetate (PVA) such as methylcellulose gum, ethyl cellulose, HYDROXY PROPYL METHYLCELLULOSE.
But, because different dispersion behaviors such as the kind of suspension agent and rerum natura are also different, can not generate good granular oil droplet, polymerization when existing suspension polymerization to begin resin do not form and generate a lot of irregular particles in the situation of particle and the resin after the polymerization, dry bad in drying process thereafter, or further problems such as mobile variation of body of powder in the course of conveying of body of powder.
But, the shape of the vinylidene chloride resin of Sheng Chenging like this, because not only can be according to the kind and the rerum natura of suspension agent, and can change because of factors such as polymerizing conditions such as the kind of initiator and addition, polymerization temperature, polymerization pressure, stirring velocity or antioxidant, lubricant, antifogging agent, stablizer, pH regulator agent, simultaneously also can various variations take place owing to the difference of the comprehensive solubleness of these materials, present situation is that why this variation takes place is unclear in theory, in fact can not grasp as the result who is caused by definite reason.
Particularly, as the monomer that becomes raw material, using boiling point is 31.7 ℃ vinylidene and at normal temperatures under the situation as the mixture of the vinyl chloride monomer of gaseous phase, to being difficult to measure under the reaction conditions beyond the behavior under atmospheric pressure of the dispersiveness of these monomeric suspension agents, infer that this is one of them reason.
In such situation, make irregular particle in the good granulous oil droplet of generation when suspension polymerization is begun, the resin after the polymerization few, in thereafter resin drying operation or carry the vinylidene chloride resin that obstacle does not take place in the operation.
Summary of the invention
Therefore; the result that the inventor furthers investigate in view of the above problems repeatedly; be in the suspension polymerization of the polyvinylidene chloride resin of reality; by will be by water; vinylidene; the mixed solution that methylcellulose gum etc. constitute stirs; the drop of the vinylidene of modest size is dispersed in the water; at this moment; cover the drop surface of vinylidene as protective membrane as the methylcellulose gum of suspension agent; play the effect that prevents that drop from merging each other; its performance is determined under the low excessively situation of lipophilicity by wetting ability and oil loving balance; methylcellulose gum is in the dissolving of a side of water, but advances out from the drop of vinylidene, and the protection of drop is died down; in addition; under the strong excessively situation of lipophilicity, methylcellulose gum enters into the drop of vinylidene, and the protection of drop is died down.Carry out polymerization if heat up when the suspension of this state is stirred, when then drop collided to each other, it is big that the frequency that drop merges each other becomes, and as its result, will have a lot of irregular particles in generating resin.
For the state in the polymerization system that makes such reality reproduces outside polymerization system, be conceived to as the mixture of vinylidene that in polymerization system, in aqueous medium, exists and vinyl chloride monomer with possess the aliphatics chlorinated hydrocarbon 1 of similarity with liquid dispersed particle, the 2-ethylene dichloride, with respect to 1, the material of the soluble part of 2-ethylene dichloride in specified range, the irregular particle that can make generation is few, the vinylidene chloride resin of obstacle does not take place in the drying process of the resin after polymerization or the conveying operation, has finished the present invention based on this knowledge.
Promptly, the manufacture method of vinylidene chloride resin of the present invention, it is characterized in that, by vinylidene chloride suspension polymerization is made in the method for vinylidene chloride resin, when above-mentioned suspension polymerization, use with respect to 1 as suspension agent, the soluble part of 2-ethylene dichloride is the methylcellulose gum of 0.1～2.0 weight %.
The working of an invention mode
The manufacturing of [I] vinylidene chloride resin
(1) starting material
(A) monomer
The monomer that uses in the manufacturing as vinylidene chloride resin, but be single vinylidene or vinylidene and with the mixture of the comonomer of its copolymerization.
(B) comonomer
But as with the comonomer of above-mentioned vinylidene copolymerization, can exemplify vinylchlorid, vinyl cyanide, vinyl acetate, vinylformic acid, methacrylic acid, methylene-succinic acid, alkyl acrylate, alkyl methacrylate, methylene-succinic acid alkyl ester etc., but be not limited to this.
Blending ratio
But with above-mentioned vinylidene chloride be principal constituent be itself and with the mixture of the comonomer of its copolymerization, specifically, preferred vinylidene chloride content is the monomer mixture of 65～98 weight %.
Can exemplify the particularly preferred vinylidene chloride of 65～98 weight % vinylidene chlorides and the mixture of vinylchlorid of containing, contain the vinylidene chloride of 85～98 weight % vinylidene chlorides and the mixture of methyl acrylate, contain the vinylidene chloride of 85～98 weight % vinylidene chlorides and the mixture of methyl methacrylate etc.
(C) initiator
In the suspension polymerization of the manufacture method of vinylidene chloride resin of the present invention,, can exemplify known radical initiator as employed initiator.
Specifically, for example can exemplify azo-compounds such as Diisopropyl azodicarboxylate, lauroyl peroxide, benzoyl peroxide, the peroxidation 2 ethyl hexanoic acid tert-butyl ester, peroxidation tert-butyl isobutyrate, the peroxidation trimethylacetic acid tert-butyl ester, butyrous radical initiators such as peroxidation dicarboxylic acid diisopropyl ester.
(D) suspension agent
(a) performance
In the manufacture method of vinylidene chloride resin of the present invention, methylcellulose gum as the suspension agent use, by cellulosic hydroxyl methoxylation is obtained, according to the position of the methoxyl group in cellulosic molecule and the degree of methoxylation, wetting ability and oil loving balance change.
As the performance of suspension agent, come the requirement wetting ability strong according to its purposes, or require lipophilicity strong.Therefore, the balance of this two aspects character is important.
It is important that the suspension agent that uses in the manufacture method of vinylidene chloride resin of the present invention possesses specific performance properties.
The methylcellulose gum that in the manufacturing of polyvinylidene chloride resin of the present invention, uses, wetting ability and oil loving balance can be passed through 1, and the ratio of the soluble part of 2-ethylene dichloride is judged.
Specifically, use is to 1, the ratio of the soluble part of 2-ethylene dichloride is the methylcellulose gum of 0.1～2.0 weight %, be with respect to 1, the methylcellulose gum that the soluble part of 2-ethylene dichloride is many, this methylcellulose gum with respect to 1, the methylcellulose gum that the soluble part of 2-ethylene dichloride is few is compared, demonstrating the affinity to vinylidene, in other words is exactly that lipophilicity is strong.
(b) with respect to 1, the soluble part of 2-ethylene dichloride
Promptly, in the manufacture method of vinylidene chloride resin of the present invention, methylcellulose gum as the suspension agent use, use is with respect to 1, and the soluble part of 2-ethylene dichloride is that the methylcellulose gum of the character of 0.1～2.0 weight %, preferred 0.3～1.8 weight %, preferred especially 0.5～1.5 weight % is important.
With respect to 1, the methylcellulose gum of the not enough above-mentioned scope of the soluble part of 2-ethylene dichloride, lipophilicity is low, though in the dissolving of water one side, advance out from the drop of vinylidene, the protection of drop is died down, and can not bring into play the performance as suspension agent.
On the other hand, use 1,2-ethylene dichloride soluble part surpasses under the situation of methylcellulose gum of above-mentioned scope, that is, under the strong excessively situation of lipophilicity, methylcellulose gum enters into the drop of vinylidene, and the protection of drop is died down.Carry out polymerization if heat up when the suspension of this state is stirred, when then drop collided to each other, it is big that the frequency that drop merges each other becomes, and as its result, can have a lot of irregular particles in generating resin.
(c) mensuration of soluble part
So-called above-mentioned with respect to 1, the soluble part of 2-ethylene dichloride, be methylcellulose gum with respect to 1, the solubleness of 2-ethylene dichloride, can be from respect to 1, the weight of the methylcellulose gum after the weight of the methylcellulose gum before the dissolving of 2-ethylene dichloride and the dissolving is calculated.
Measuring method
As in the above-mentioned methylcellulose gum with respect to 1, the measuring method of the soluble part of 2-ethylene dichloride, by be determined at 25 ℃ to 1, the weight of the methylcellulose gum before the dissolving of 2-ethylene dichloride and with respect to 1, the weight of the methylcellulose gum after the dissolving of 2-ethylene dichloride and carrying out.
(E) aqueous medium
Aqueous medium as using when the above-mentioned suspension polymerization makes water, particularly deionized water.
(F) other Synergist S-421 95s
Can use chain-transfer agent, pH regulator agent, Synergist S-421 95s such as stablizer.
(2) suspension polymerization
In the presence of above-mentioned vinylidene, comonomer, initiator, suspension agent, aqueous medium, can indistinguishably implement with the condition of in the manufacture method of common vinylidene chloride resin, carrying out.Specifically, for example under the condition of the polymerization pressure of 20～80 ℃ polymerization temperature, normal pressure～1MPa, adopt intermittent type or continous way to carry out suspension polymerization.
Suspension polymerization adopts tank reactor to carry out usually.
[II] vinylidene chloride resin
(1) kind
In the manufacture method of vinylidene chloride resin of the present invention, as the vinylidene chloride resin of making, be resin, for example based on vinylidene chloride, the polyvinylidene dichloride resin of homopolymer, but other monomeric binary or terpolymers of vinylidene chloride and copolymerization.
Specifically, for example can enumerate the polyvinylidene dichloride resin, or vinylidene chloride-vinyl chloride copolymer resin, or vinylidene chloride-acrylic copolymer resin, vinylidene chloride-Sipacril 2739OF resin, vinylidene chloride-methyl acrylate copolymer resin, vinylidene chloride-methylmethacrylate copolymer resin etc., or vinylidene chloride-vinylchlorid-acrylic copolymer resin, vinylidene chloride-vinyl chloride methacrylic acid resin, vinylidene chloride-vinyl chloride-methyl acrylate copolymer resin, vinylidene chloride-vinyl chloride methyl methacrylate resin etc.
Monomer content
Content as each monomeric unit in these copolymer resins, be generally the copolymer resin of the vinylchlorid of the vinylidene chloride of 65～95 weight % and 35～5 weight %, but the vinylchlorid of the vinylidene chloride of 65～95 weight % and 34.5～4.5 weight % and other monomeric copolymer resins 0.5～8.0 weight % and their copolymerization.
(2) shape
The vinylidene chloride resin that obtains by above-mentioned suspension polymerization carries out polymerization, so obtain with single spherolite of spherical shape under the dispersion state of mixture droplets nonjoinder in aqueous medium of monomer and polymerization starter.
And, can under the situation below the 10 weight %, below the preferred 7 weight % of being generated as of the irregular particle of the shape different, make vinylidene chloride resin with common particle shape.
The shape of irregular particle
The shape of the irregular particle among so-called the present invention, the ratio (long diameter/weak point diameter) that is long diameter and short diameter is in the shape more than 1.05.
(3) Synergist S-421 95
In the manufacture method of vinylidene chloride resin of the present invention, in the vinylidene chloride resin of manufacturing, can cooperate additives such as plasticizer, thermo-stabilizer, processing aid, photostabilizer, UV light absorber, antioxidant, antistatic agent, tensio-active agent, pigment, lubricant, anti-hard caking agent, antifogging agent, antioxidant, white dyes, weighting agent.
(4) physical properties
The vinylidene chloride resin of above-mentioned shape because the irregular particle that generates is few, forms uniform single spherolite, so even mix with pigment or additive, also can not take place because bad color spot that causes of mixing or smoothness are bad.
Embodiment
Below by embodiment and comparative example, the present invention is carried out more specific description.
[I] evaluation method
(1) with respect to 1, the soluble part of 2-ethylene dichloride
As in the above-mentioned methylcellulose gum with respect to 1, the measuring method of the soluble part of 2-ethylene dichloride while be to stirring 1 of attemperation in 25 ℃ Water Tank with Temp.-controlled, drops into the test portion 3g of weighing in the 2-ethylene dichloride, stir and made its dissolving in 3 hours.
After the dissolving, use the Whatman suction filtration, with its filtrate evaporation drying.Quality before and after dry is obtained to 1 the amount of the soluble part of 2-ethylene dichloride.
Will be to 1, the amount of the soluble part of 2-ethylene dichloride is used with respect to the weight percent of test portion integral body and is represented.
(2) irregular particle ratio
As the measuring method of the irregular particle ratio in the vinylidene chloride resin, will sieve vibrator (vibrating sand tube number (beating number) 137 times/minute 240 times/minute) with Luo Taipushi with the test portion that antistatic agent is handled and carry out the dry type screening, be classified into different granularities.
Sieve uses JIS Z8801 standard sieve (355 μ m, 250 μ m, 180 μ m, 150 μ m, 106 μ m, 75 μ m, 63 μ m, 45 μ m).
Different grain size is taken microphotograph, and number goes out irregular particle (not being the particle of single spheroid), obtains the ratio of the irregular particle in all particles.
[II] embodiment and comparative example
Embodiment 1
In 150 liters the stainless steel reactive tank that possesses paddle stirrer, the 81kg that packs into dissolved 67.5g to 1, the soluble part of 2-ethylene dichloride is the deionized water of the methylcellulose gum of 0.6 weight %, after nitrogen displacement space region, with dissolved the 54kg vinylidene of 75g peroxidation dimethyl isopropyl ester and 13.55kg vinyl chloride monomer the mixture input wherein.
After their mixture mixed with the stirring velocity of the particle dia that reaches regulation, be warming up to 35 ℃ of beginning polyreactions.
, Yi Bian one side continuously be warming up to 50 ℃ continue polymerization 50 hour after, the vinylidene chloride resin slurries that generate from reactor taken out thereafter, dehydration, drying obtains vinylidene chloride resin.
The evaluation result of the vinylidene chloride resin of gained is shown in table 1.
Embodiment 2
Except using 1, the soluble part of 2-ethylene dichloride is beyond the methylcellulose gum of 1.5 weight %, and all the other and embodiment 1 implement in the same manner.
The evaluation result of the vinylidene chloride resin of gained is shown in table 1.
Comparative example 1
Except using 1, the soluble part of 2-ethylene dichloride is beyond the methylcellulose gum of 2.5 weight %, and all the other and embodiment 1 implement in the same manner.
The evaluation result of the vinylidene chloride resin of gained is shown in table 1.
Embodiment 3
In 150 liters the stainless steel reactive tank that possesses paddle stirrer, the 81kg that packs into dissolved 67.5g to 1, the soluble part of 2-ethylene dichloride is the deionized water of the methylcellulose gum of 0.6 weight %, after nitrogen displacement space region, wherein with the mixture input of having dissolved the 64kg vinylidene of the 225g peroxidation trimethylacetic acid tert-butyl ester and 3.5kg methacrylate monomer.
After their mixture mixed with the stirring velocity of the particle dia that reaches regulation, be warming up to 70 ℃ of beginning polyreactions.
, this temperature under continue polymerization 10 hour after, the vinylidene chloride resin slurries that generate from reactor taken out thereafter, dehydration, drying obtains vinylidene chloride resin.
The evaluation result of the vinylidene chloride resin of gained is shown in table 1.
Comparative example 2
Except using 1, the soluble part of 2-ethylene dichloride is beyond the methylcellulose gum of 2.2 weight %, and other and embodiment 3 implement in the same manner.
The evaluation result of the vinylidene chloride resin of gained is shown in table 1.
Table 1
Utilize possibility on the industry
The manufacture method of vinylidene chloride resin of the present invention like this, the irregular particle of generation is few, shape Become uniform single spherolite, therefore can make bad the causing of mixing that is difficult to take place owing to pigment or additive Color spot or the level and smooth bad vinylidene chloride resin of property, be in industrial very useful method therefore.
Claims (3)
1. the manufacture method of a vinylidene chloride resin, it is characterized in that, making by the suspension polymerization vinylidene chloride in the method for vinylidene chloride resin, but using aqueous medium suspension polymerization vinylidene and during with the mixture of the comonomer of its copolymerization, use radical initiator as initiator, use with respect to 1 as suspension agent, the soluble part of 2-ethylene dichloride is the methylcellulose gum of 0.1～2.0 weight %, and the content of vinylidene chloride is 65-98 weight % in the said mixture.
2. according to the manufacture method of the vinylidene chloride resin of claim 1 record, wherein, the ratio of the irregular particle in the vinylidene chloride resin of generation is below the 10 weight %.
3. according to the manufacture method of the vinylidene chloride resin of claim 1 record, wherein, under 20-80 ℃ temperature, carry out above-mentioned suspension polymerization.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP339304/2001 | 2001-11-05 | ||
| JP339304/01 | 2001-11-05 | ||
| JP2001339304A JP2003137911A (en) | 2001-11-05 | 2001-11-05 | Method for producing vinylidene chloride-based resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1417237A CN1417237A (en) | 2003-05-14 |
| CN100408604C true CN100408604C (en) | 2008-08-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021410054A Expired - Fee Related CN100408604C (en) | 2001-11-05 | 2002-05-10 | Production process of vinylidene chloride resin |
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| JP (1) | JP2003137911A (en) |
| CN (1) | CN100408604C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009120630A (en) * | 2007-11-12 | 2009-06-04 | Asahi Kasei Chemicals Corp | Method for producing vinylidene chloride-based copolymer, and vinylidene chloride-based copolymer |
| JP5938279B2 (en) * | 2012-06-19 | 2016-06-22 | 株式会社クレハ | Method for producing aqueous cellulose solution |
| CN104619769A (en) * | 2012-10-01 | 2015-05-13 | 株式会社吴羽 | Vinylidene chloride-based copolymer resin composition and molded product thereof |
| TWI598382B (en) * | 2013-08-27 | 2017-09-11 | Kureha Corp | Vinylidene chloride resin film and its manufacturing method |
| US10059830B2 (en) * | 2013-11-11 | 2018-08-28 | Dow Global Technologies Llc | Process to produce a vinylidene chloride-based heteropolymer |
| JP7105713B2 (en) * | 2019-03-18 | 2022-07-25 | 株式会社クレハ | Resin film and its manufacturing method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6295309A (en) * | 1985-10-22 | 1987-05-01 | Japan Synthetic Rubber Co Ltd | Production of impact-resistant aromatic vinyl resin |
| EP0526216A2 (en) * | 1991-08-01 | 1993-02-03 | Kureha Chemical Industry Co., Ltd. | Method of making vinylidene fluoride polymer |
| JPH05295008A (en) * | 1991-06-21 | 1993-11-09 | Nippon Zeon Co Ltd | Suspension polymerization of vinyl chloride-based monomer |
-
2001
- 2001-11-05 JP JP2001339304A patent/JP2003137911A/en active Pending
-
2002
- 2002-05-10 CN CNB021410054A patent/CN100408604C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6295309A (en) * | 1985-10-22 | 1987-05-01 | Japan Synthetic Rubber Co Ltd | Production of impact-resistant aromatic vinyl resin |
| JPH05295008A (en) * | 1991-06-21 | 1993-11-09 | Nippon Zeon Co Ltd | Suspension polymerization of vinyl chloride-based monomer |
| EP0526216A2 (en) * | 1991-08-01 | 1993-02-03 | Kureha Chemical Industry Co., Ltd. | Method of making vinylidene fluoride polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1417237A (en) | 2003-05-14 |
| JP2003137911A (en) | 2003-05-14 |
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