CN100368451C - Method of impact modifier in acr in use for synthesizing polyvinyl chloride in one-step - Google Patents
Method of impact modifier in acr in use for synthesizing polyvinyl chloride in one-step Download PDFInfo
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- CN100368451C CN100368451C CNB2005100444431A CN200510044443A CN100368451C CN 100368451 C CN100368451 C CN 100368451C CN B2005100444431 A CNB2005100444431 A CN B2005100444431A CN 200510044443 A CN200510044443 A CN 200510044443A CN 100368451 C CN100368451 C CN 100368451C
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- butyl acrylate
- methyl methacrylate
- agglomerant
- reaction
- impact modifier
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Abstract
This invention discloses one-step method for synthesizing acrylate anti-impact modifier for polyvinyl chloride products. The acrylate anti-impact modifier is synthesized from methyl methacrylate 10-50 wt. % and n-butyl acrylate 50-90 wt. % by emulsion polymerization. The method comprises: (1) reacting n-butyl acrylate at 60-80 deg.C in alkaline condition (pH = 7-10), and adding an agglomerant when the conversion rate is 10-15%; (2) adding methyl methacrylate when the conversion rate is higher than 97%; (3) spray-drying the reaction products. The amount of the agglomerant is 0.1-1 wt. % of n-butyl acrylate, and the agglomerant can be acrylic acid, methacrylic acid, magnesium sulfate, sodium chloride or calcium chloride. The method has such advantages as simple process, easy control, uniform particle size distribution and stable performance.
Description
Technical field
The present invention relates to improve the synthetic method of the acrylic ester impact-resisting modifier of polrvinyl chloride product resistance to impact shock.
Background technology
The polyvinyl-chloride use acrylic ester impact-resisting modifier is to form (being called for short the ACR resin) by methyl methacrylate and n-butyl acrylate letex polymerization, is domestic a kind of novel PVC toughner of developing in recent years.Its synthesis technique generally adopts letex polymerization, earlier synthetic seed latex, the method for hole enlargement again.Its complex manufacturing, long flow path, the reference mark is many, and operation easier is big, and the production cycle is long, and size distribution is wide, and product stability is poor.
Summary of the invention
Technical problem to be solved by this invention provides a kind of method of one-step synthesis polyvinyl-chloride use acrylic ester impact-resisting modifier, simplifies processing method, shortens the production cycle, and size distribution is even, and product performance are stable.
The method of one-step synthesis polyvinyl-chloride use acrylic ester impact-resisting modifier of the present invention, form by methyl methacrylate and n-butyl acrylate letex polymerization, it is characterized in that under pH is 7～10 condition, n-butyl acrylate is 60～80 ℃ of reactions down, when reaction conversion ratio reaches 10～15%, add agglomerant, when reaction conversion ratio reach 〉=97% the time, add methyl methacrylate, discharging spraying drying after reaction is finished, wherein the total mass in methyl methacrylate and n-butyl acrylate is 100%, methyl methacrylate accounts for 10～50%, n-butyl acrylate accounts for 50～90%, and agglomerant is 0.1～1% of a n-butyl acrylate amount.
Described agglomerant can be vinylformic acid, methacrylic acid, sal epsom, sodium-chlor or calcium chloride.
The present invention is an emulsion polymerization still, and the emulsifying agent that is adopted in the emulsion polymerization is generally 1～2% of reaction monomers total amount, and oxygenant is generally 0.01～0.1% of reaction monomers total amount.Emulsifying agent and oxygenant all adopt the component of the common usefulness of emulsion polymerization, are sodium lauryl sulphate as emulsifying agent, and oxygenant adopts Potassium Persulphate or ammonium persulphate.
Reaction process of the present invention passes through to add the emulsion of the mode one-step synthesis of agglomerant to the anti-impact ACR of required particle diameter, gets product through spraying drying then.This processing method is simple, and control is convenient, shortens the production cycle greatly, and size distribution is even, and product performance are stable.
Embodiment
Embodiment one:
In 3000L enamel glass reactor, add the 1500kg softening water, emulsifier sodium lauryl sulfate 20kg, start and stir, add sodium bicarbonate 1.5kg, add monomer n-butyl acrylate 1000kg then, when opening reacting kettle jacketing steam temperature in the kettle being risen to 58～60 ℃, add oxygenant Potassium Persulphate 2kg, control is reflected at reaction between 60～80 ℃, reaction is surveyed transformation efficiency every sampling in 30 minutes, when transformation efficiency reaches 10～15%, add agglomerant vinylformic acid 1.0kg, react about 4 hours after, when the transformation efficiency of monomer n-butyl acrylate reaches 97%, add 250kg methyl methacrylate reaction after 2 hours discharging be drying to obtain finished product.
Embodiment two:
According to the method for embodiment one, monomer n-butyl acrylate 750kg, agglomerant are sal epsom 3.75kg, monomers methyl methacrylate 500kg.
Embodiment three:
According to the method for embodiment one, monomer n-butyl acrylate 1125kg, agglomerant are sodium-chlor 11.25kg, and monomers methyl methacrylate 125kg, methyl methacrylate add when the transformation efficiency of monomer n-butyl acrylate reaches 100%.
The below comparison of the finished product that makes for traditional technology and one-step technology of the present invention:
The general seed that makes in enamel reaction still earlier of traditional technology letex polymerization seed latex diameter expansion method makes anti-impact ACR finished product B with in second still with the seed hole enlargement again.
The comparison of the finished product B that synthetic anti-impact ACR resin finished product A of single stage method of the present invention and letex polymerization seed latex diameter expansion method make:
With following two assembly sides respectively according to part by weight in high speed mixer to 125 ℃ of dischargings cooling, then under 180 ℃ of conditions of 3 minutes on the double roller plastic-making device, be drawn into sheet material, the sheet material that makes is pressed into sheet material respectively on the compression molding instrument, sheet material is made the batten of surveying its notch shock experiment and stretching experiment on omnipotent sampling machine, carry out the detection of tensile strength and shock strength respectively.
To fill a prescription 1 and prescription 2 on torque rheometer, survey its processing characteristics respectively.
Formula table
| Prescription 1 | Prescription 2 | |
| PVC | 100 | 100 |
| The dibasic plumbous sulfite | 3.5 | 3.5 |
| Lead stearate | 1.0 | 1.0 |
| Calcium stearate | 0.5 | 0.5 |
| Stearic acid | 0.02 | 0.02 |
| Oxidized polyethlene wax | 0.015 | 0.015 |
| Titanium dioxide | 4 | 4 |
| Lime carbonate | 10 | 10 |
| The ACR processing aid | 2 | 2 |
| Finished product A | 7 | |
| Finished product B | 7 |
Detected result
| Prescription 1 | Prescription 2 | ||
| Notched Izod impact strength KJ/m 2 | 20.57 | 20.68 | |
| Elongation at break % | 173 | 172 | |
| Tensile strength N/m 2 | 41.35 | 41.56 | |
| Processing characteristics | Peak torque | 33.5 | 33.3 |
| Minimal torque | 18.0 | 18.2 | |
| Balancing torque | 27.1 | 27.1 | |
| Fusion time | 101 | 102 | |
The generated time of finished product A and finished product B result relatively
| Finished product A | Finished product B | |
| Generated time | 4 | 12 |
By the result as seen, the single stage method synthesizing polyvinyl chloride has shortened generated time significantly with the novel process of acrylic ester impact-resisting modifier ACR resin, and can reach the same service requirements of ACR that makes with letex polymerization seed latex diameter expansion method fully.
Claims (3)
1. the method for one-step synthesis polyvinyl-chloride use acrylic ester impact-resisting modifier, form by methyl methacrylate and n-butyl acrylate letex polymerization, it is characterized in that under pH is 7～10 condition, n-butyl acrylate is 60～80 ℃ of reactions down, when reaction conversion ratio reaches 10～15%, add agglomerant, when reaction conversion ratio reach 〉=97% the time, add methyl methacrylate, discharging spraying drying after reaction is finished, wherein the total mass in methyl methacrylate and n-butyl acrylate is 100%, methyl methacrylate accounts for 10～50%, n-butyl acrylate accounts for 50～90%, and agglomerant is 0.1～1% of a n-butyl acrylate amount.
2. method according to claim 1 is characterized in that described agglomerant is vinylformic acid, methacrylic acid, sal epsom, sodium-chlor or calcium chloride.
3. method according to claim 1 is characterized in that adding emulsifying agent and oxygenant in the emulsion polymerization, and emulsifying agent is 1～2% of a reaction monomers total mass, and oxygenant is 0.01～0.1% of a reaction monomers total mass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100444431A CN100368451C (en) | 2005-08-19 | 2005-08-19 | Method of impact modifier in acr in use for synthesizing polyvinyl chloride in one-step |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100444431A CN100368451C (en) | 2005-08-19 | 2005-08-19 | Method of impact modifier in acr in use for synthesizing polyvinyl chloride in one-step |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1916043A CN1916043A (en) | 2007-02-21 |
| CN100368451C true CN100368451C (en) | 2008-02-13 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100444431A Expired - Fee Related CN100368451C (en) | 2005-08-19 | 2005-08-19 | Method of impact modifier in acr in use for synthesizing polyvinyl chloride in one-step |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100368451C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262804B (en) * | 2014-10-15 | 2016-04-06 | 山东世拓高分子材料股份有限公司 | PVC pipe goods impact modifier compositions and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1357557A (en) * | 2000-12-14 | 2002-07-10 | 中国石化集团齐鲁石油化工公司 | Production process of impact-resisting and heat resistant copolymerized resin |
| WO2002090404A1 (en) * | 2001-05-02 | 2002-11-14 | Kaneka Corporation | Rubber-modified resin and thermoplastic resin composition containing the same |
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2005
- 2005-08-19 CN CNB2005100444431A patent/CN100368451C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1357557A (en) * | 2000-12-14 | 2002-07-10 | 中国石化集团齐鲁石油化工公司 | Production process of impact-resisting and heat resistant copolymerized resin |
| WO2002090404A1 (en) * | 2001-05-02 | 2002-11-14 | Kaneka Corporation | Rubber-modified resin and thermoplastic resin composition containing the same |
Non-Patent Citations (1)
| Title |
|---|
| 共聚型丙烯酸酯抗冲改性剂的合成及其对PVC的改性. 杨敏等.塑料工业，第30卷第4期. 2002 * |
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| CN1916043A (en) | 2007-02-21 |
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