CN101659723A - Styrene-acryonitrile copolymer for modifying ABS and PVC resins - Google Patents
Styrene-acryonitrile copolymer for modifying ABS and PVC resins Download PDFInfo
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- CN101659723A CN101659723A CN200910018971A CN200910018971A CN101659723A CN 101659723 A CN101659723 A CN 101659723A CN 200910018971 A CN200910018971 A CN 200910018971A CN 200910018971 A CN200910018971 A CN 200910018971A CN 101659723 A CN101659723 A CN 101659723A
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Abstract
The invention discloses a styrene-acryonitrile copolymer for modifying ABS and PVC resins and a preparation method thereof, belonging to the technical field of macromolecular composite compound. The preparation method is characterized by using a segment emulsion polymerization process, controlling the polymerization temperature between 40 DEG C and 91 DEG C in the presence of an emulsifying agent,an initiating agent and a molecular weight regulator to prepare a copolymerization emulsion; and the emulsion is dried by spraying to prepare a solid powder product, wherein the total weight of the copolymerization monomer is counted as 100 percent, the styrene accounts for 60 percent to 90 percent, the acryonitrile accounts for 10 percent to 40 percent, and the weight ratio of the total weight of the copolymerization monomer and the water is 0.01-2.5:1. The invention remarkably improves the plasticizing processing performance and the fusant intensity of the ABS and PVC resins with stable andcontrollable foaming. The modified ABS and PVC resin product has high surface gloss and anti-drawing intensity, no discoloration under high temperature and favorable heat-resistant performance.
Description
Technical field
The present invention is styrene-acrylonitrile copolymer of a kind of ABS of being used for and polyvinyl chloride resin modification and preparation method thereof, belongs to technical field of macromolecular composite compound.
Background technology
Acrylonitrile-butadiene-styrene copolymer ABS and polyvinylchloride, have corrosion-resistant, superiority such as plasticity is good, and forming process is flexible, cost is low.At car and boat, aircraft manufacturing, construction work, electrical component, all many-sides such as office supplies articles for use, medicine equipment are used widely.But owing to be subjected to many limitations such as feed composition, polymerization technique, the problem that can not meet consumers' demand at ubiquity aspect processing characteristics such as heat-resistant stability, impact strength, processing fluidity, low-temperature flexibility and the mechanical property.
ABS is as a kind of engineering plastics, and it is low in use to exist melt strength, the problem that product surface smooth finish is relatively poor; In PVC uses, also do not exist plasticizing capacity good and melt strength is lower and many defectives of foaming stable and controllable aspect, affect with ABS and polyvinyl chloride resin is the internal performance and the outward appearance of the various products made of raw material always.
In the thermoplastic resin course of processing, add properties-correcting agent, form various engineering plastic alloys, be in the prior art, be used to one of method of improving the thermoplastic resin performance.Styrene-acrylonitrile copolymer is used as pvc pipe material frothing aid.But be used for the ABS modification and yet there are no report.But because styrene-acrylonitrile copolymer molecular-weight average of the prior art is not high enough, and the range of molecular weight distributions broad, cause modified effect not good.
A kind of plasticizing processing characteristics, melt strength that can significantly improve ABS and polyvinyl chloride resin, the foaming stable and controllable, make that ABS after the modification and polyvinyl chloride resin product have high surface gloss and tensile strength, high-temperature stable nondiscoloration, ideal that resistance toheat is good is used for styrene-acrylonitrile copolymer of ABS and polyvinyl chloride resin modification and preparation method thereof, is that people expect.
Summary of the invention
The objective of the invention is to avoid above-mentioned weak point of the prior art, and provide a kind of plasticizing processing characteristics, melt strength that can significantly improve ABS and polyvinyl chloride resin, the foaming stable and controllable makes ABS after the modification and polyvinyl chloride resin product have the styrene-acrylonitrile copolymer that high surface gloss and tensile strength, high-temperature stable nondiscoloration, ideal that resistance toheat is good are used for ABS and polyvinyl chloride resin modification.
Purpose of the present invention can reach by following measure:
The styrene-acrylonitrile copolymer that is used for ABS and polyvinyl chloride resin modification of the present invention is characterized in that:
A. adopt segmentation emulsion polymerization technique method, emulsifying agent, initiator, molecular weight regulator, in the presence of, control in 40 ℃ of-91 ℃ of temperature ranges the preparation emulsion; After emulsion is spray-dried again, make the pressed powder product;
B. wherein comonomer (vinylbenzene and vinyl cyanide) gross weight is 100%, styrene comprise 60-90%, and vinyl cyanide accounts for 10-40%, and the weight ratio of comonomer monomer total amount and water is 0.01～2.5: 1.Monomer styrene accounts for 60～90% of monomer content, and is preferred 65～85%, and more preferably 65～80%, preferred especially 65～75%; Vinyl cyanide is 10～40% of a monomer content, and is preferred 15～35%, more preferably 20～35%, preferred especially 25～35%.
Emulsion polymerization technique has successfully solved the thickness problem of mass polymerization and solution polymerization material, the selection of monomeric component and proportioning and the use of proper auxiliary agent, and can adopt segmentation (as three sections) emulsion polymerization technique method to guarantee ultra-high molecular weight and the narrower styrene-acrylonitrile copolymer of molecular weight distribution, ultra-high molecular weight, mobile fabulous SAN have promoted the flowability of ABS, optimized processing characteristics, improved product surface mechanical property such as smooth finish, tensile strength, guaranteed the heat-resisting stable nondiscoloration of product.Product molecular-weight average (number average) is between 5,000,000-1,000 ten thousand.
Equally, when being used as the processing aid use of PVC, promote the plasticizing of PVC, increased melt strength.When being used for the PVC foaming control agent, promoted the melt strength and the ductility of PVC plasticizing, fusion, raising foaming product, made the foaming process stable and controllable, thereby obtain the even tiny density materials with smaller of foam structure.Because the second-order transition temperature of this polymkeric substance is higher than the second-order transition temperature of PVC, as the heat-proof modifier use of PVC, effect highly significant.
Purpose of the present invention can also reach by following measure:
The emulsifying agent that the styrene-acrylonitrile copolymer that is used for ABS and polyvinyl chloride resin modification of the present invention, letex polymerization adopt is known any one or its any two or more combinations that choose from alkyl-sulphate, alkylphosphonic, alkylbenzene sulfonate, Voranol EP 2001, polyxyethylated fatty acid ester; Consumption is 0.1～8% of a comonomer consumption.
The styrene-acrylonitrile copolymer that is used for ABS and polyvinyl chloride resin modification of the present invention, the emulsifying agent that letex polymerization is adopted is the compound of known anionic emulsifier or anionic emulsifier and nonionic emulsifying agent.Consumption is the 0.5%-3.0% of comonomer weight;
The styrene-acrylonitrile copolymer that is used for ABS and polyvinyl chloride resin modification of the present invention, the initiator that letex polymerization is adopted is known any one (oxygenant) that chooses from persulphate, organo-peroxide, azo compound, or the redox initiator system of being formed with any one (reductive agent) of from sulphite, hydrosulphite, thiosulphate, choosing, consumption is the 0.001-1% of comonomer weight.
The styrene-acrylonitrile copolymer that is used for ABS and polyvinyl chloride resin modification of the present invention, the molecular weight regulator that letex polymerization is adopted are to adopt C
4-C
20Alkyl sulfhydryl, its consumption are (0-0.5%) of comonomer weight, preferred 0.1-0.5%.
Segmentation emulsion polymerisation process of the present invention can be according to the technique known method, and the consumption of every kind of polymerization single polymerization monomer can be the same or different in every section.
Technical scheme of the present invention has outstanding substantive distinguishing features and obvious improvement compared to existing technology, and technical scheme will produce following positively effect after implementing:
1. a kind of plasticizing processing characteristics, melt strength that can significantly improve ABS and polyvinyl chloride resin is provided, the foaming stable and controllable makes ABS after the modification and polyvinyl chloride resin product have high surface gloss and tensile strength, high-temperature stable nondiscoloration, ideal that resistance toheat is good is used for styrene-acrylonitrile copolymer of ABS and polyvinyl chloride resin modification and preparation method thereof.
2. can adopt segmentation emulsion polymerization technology, suitable monomers proportioning and the auxiliary agent that matches have prepared ultra-high molecular weight and the narrower polymkeric substance of molecular weight distribution.
3. be used for ABS resin, successful solution the melt strength that exists in its use low, the problem that product surface smooth finish is relatively poor.
4. be used for the low foamed forming process of rigid polyvinyl chloride, it is wrapped on the macromole of polyvinyl chloride with the form of molecule, form reticulated structure, thereby play the plasticizing that promotes polyvinyl chloride, the effect that improves products surface quality and improve melt strength and extensibility makes material obtain fine and close foam structure and good appearance.
5. the other materials that is used for PVC, because the second-order transition temperature of this polymkeric substance is higher than the second-order transition temperature of PVC, the heat-proof modifier that can be used as PVC uses.
6. preparation technology is simple, and production cost is low, and product is easy to use.
Embodiment
The present invention is described in further detail below in conjunction with embodiment:
Embodiment 1-7 and Comparative Examples 1-2:
Be used for the preparation method of the styrene-acrylonitrile copolymer of ABS and polyvinyl chloride resin modification, comprise the steps:
A. pre-emulsification: draft vinylbenzene, vinyl cyanide, emulsifying agent, molecular weight regulator, the deionized water that prescription uses three sections letex polymerizations respectively according to table 1 and drop in the reactor, room temperature, high-speed stirring emulsification 0.5-1 hour, form stable emulsion, suction is scale tank separately, blanketing with inert gas, standby;
B. segmentation letex polymerization: stir down,, drop in the polymerization reaction kettle, add the oxygenant of one section initiator of metering with one section pre-emulsion of step a preparation; Under the nitrogen protection, be warming up to 40 ℃-80 ℃, add the reductive agent of metering, controlled temperature is 60～70 ℃ of polymerizations, after reaction finishes; Add second section pre-emulsion and corresponding oxygenant, reductive agent, under 70～75 ℃ of temperature, polymerization; After reaction finishes, add the 3rd section pre-emulsion and corresponding oxygenant, reductive agent again, controlled temperature is 75～85 ℃ of polymerizations, after reaction finishes, is warming up to 90 ± 1 ℃ of insulations, slaking 1-2 hour.Be cooled to 40 ℃, filter the styrene-acrylonitrile copolymer emulsion, polymerisation conversion is 99.5%, molecular-weight average 5,000,000-1,000 ten thousand is standby;
The styrene-acrylonitrile copolymer emulsion of c. spraying, drying: step b preparation is spray-dried, can obtain the white powder shaped polymer.
D. quality test, qualified after, the packing, the warehouse-in.
Table 1 embodiment 1-7, Comparative Examples 1-2 parts by weight of raw materials and product performance index
| Raw material | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Comparative Examples 1 | Comparative Examples 2 |
| One section letex polymerization | |||||||||
| Vinylbenzene | ??90 | ??80 | ??75 | ??80 | ??65 | ??70 | ??62 | ??90 | ??62 |
| Vinyl cyanide | ??10 | ??20 | ??25 | ??20 | ??35 | ??30 | ??38 | ??10 | ??38 |
| Sodium lauryl sulphate | ??3 | ??2 | ??3 | ??2 | ??3 | ??2 | ??2 | ??3 | ??3 |
| Lauryl mercaptan | ??0.01 | ??0.005 | ??0.005 | ??0.01 | ??0.003 | ??0.003 | ??0.003 | ??0.01 | ??0.01 |
| Potassium Persulphate | ??0.2 | ??0.2 | ??0.2 | ??0.2 | ??0.2 | ??0.2 | ??0.2 | ??0.2 | ??0.2 |
| Sodium bisulfite | ??0.6 | ??0.6 | ??0.6 | ??0.6 | ??0.6 | ??0.6 | ??0.6 | ??0.6 | ??0.6 |
| Water | ??200 | ??200 | ??200 | ??200 | ??200 | ??200 | ??200 | ??200 | ??200 |
| Two sections letex polymerizations | |||||||||
| Vinylbenzene | ??80 | ??80 | ??75 | ??75 | ??70 | ??75 | ??70 | ??90 | ??62 |
| Vinyl cyanide | ??20 | ??20 | ??25 | ??25 | ??30 | ??25 | ??30 | ??10 | ??38 |
| Sodium lauryl sulphate | ??1 | ??1.5 | ??1 | ??1.5 | ??1 | ??1.2 | ??1 | ??1 | ??1 |
| Lauryl mercaptan | ??0.01 | ??0.01 | ??0.005 | ??0.005 | ??0.003 | ??0.003 | ??0.003 | ??0.01 | ??0.01 |
| Potassium Persulphate | ??0.2 | ??0.4 | ??0.2 | ??0.6 | ??0.2 | ??0.3 | ??0.2 | ??0.2 | ??0.2 |
| Sodium bisulfite | ??0.6 | ??0.6 | ??0.6 | ??0.6 | ??0.6 | ??0.6 | ??0.6 | ??0.6 | ??0.6 |
| Water | ??100 | ??100 | ??100 | ??100 | ??100 | ??100 | ??100 | ??100 | ??100 |
| Three sections letex polymerizations | |||||||||
| Vinylbenzene | ??70 | ??80 | ??75 | ??70 | ??90 | ??70 | ??80 | ??90 | ??70 |
| Vinyl cyanide | ??30 | ??20 | ??25 | ??30 | ??10 | ??30 | ??20 | ??10 | ??30 |
| Sodium lauryl sulphate | ??1 | ??1 | ??1 | ??1 | ??1 | ??1 | ??1 | ??1 | ??1 |
| Lauryl mercaptan | ??0.002 | ??0.002 | ??0.003 | ??0.001 | ??0.005 | ??0.001 | ??0.002 | ??0.002 | |
| Potassium Persulphate | ??0.2 | ??0.3 | ??0.2 | ??0.2 | ??0.3 | ??0.2 | ??0.2 | ??0.2 | ??0.2 |
| Sodium bisulfite | ??0.6 | ??0.6 | ??0.6 | ??0.6 | ??0.6 | ??0.6 | ??0.6 | ??0.6 | ??0.6 |
| Water | ??100 | ??100 | ??100 | ??100 | ??100 | ??100 | ??100 | ??100 | ??100 |
| Polymerisation conversion % | ??99.8 | ??99.7 | ??99.7 | ??99.8 | ??99.5 | ??99.8 | ??99.6 | ??99.8 | ??98.9 |
| Molecular-weight average (ten thousand) | ??500 | ??700 | ??1000 | ??800 | ??900 | ??800 | ??900 | ??500 | ??700 |
| Vicat softening point ℃ | ??100 | ??102 | ??105 | ??106 | ??108 | ??110 | ??109 | ??100 | ??112 |
Product performance:
The finished product of the foregoing description 1-7 and Comparative Examples 1-2 gained is mixed in high speed mixer respectively to 110 ℃ of discharging coolings according to following 2 kinds of prescriptions, the extrusion moulding test is done in the back under the condition of 170 ℃ of extruder temperatures, respectively the foam performance of PVC foaming plate and the processing characteristics of ABS are detected detected result such as table 2
1.PVC foaming plate prescription
PVC(s-700)：??????100
Stablizer: 4.5
Lime carbonate: 10
Titanium dioxide: 4
OPE：?????????????0.5
AC-316：??????????0.4
AC whipping agent: 0.8
Multipolymer auxiliary agent of the present invention: 10
ZB-60：???????????0.7
2.ABS processing formula
ABS high glue powder: 40
AS resin: 56
Multipolymer auxiliary agent of the present invention: 4
Oxidation inhibitor: 0.4
Table 2 experimental test result
| Processing characteristics | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Comparative Examples 1 | Comparative Examples 2 |
| The PVC foam performance | Better | Better | Better | Good | Good | Good | Good | Difference | Relatively poor |
| The ABS processing characteristics | Better | Better | Better | Good | Good | Good | Better | Relatively poor | Difference |
Claims (7)
1. styrene-acrylonitrile copolymer that is used for ABS and polyvinyl chloride resin modification is characterized in that:
Adopt segmentation emulsion polymerization technique method, in the presence of emulsifying agent, initiator, molecular weight regulator, polymerization temperature is controlled between 40 ℃-91 ℃, the preparation copolymer emulsion after emulsion is spray-dried again, makes the pressed powder product, wherein the comonomer gross weight is 100%, styrene comprise 60-90%, vinyl cyanide accounts for 10-40%, and the weight ratio of comonomer total amount and water is 0.01～2.5: 1.
2. according to the styrene-acrylonitrile copolymer that is used for ABS and polyvinyl chloride resin modification of claim 1, it is characterized in that emulsifying agent that letex polymerization is adopted is any one or its any two or more combinations that choose from alkyl-sulphate, alkylphosphonic, alkylbenzene sulfonate, Voranol EP 2001, polyxyethylated fatty acid ester, consumption is the 0.1-8% of comonomer weight.
3. according to the styrene-acrylonitrile copolymer that is used for ABS and polyvinyl chloride resin modification of claim 1, it is characterized in that the emulsifying agent that letex polymerization is adopted is the compound of anionic emulsifier or anionic emulsifier and nonionic emulsifying agent, consumption is the 0.5%-3.0% of comonomer weight.
4. according to the styrene-acrylonitrile copolymer that is used for ABS and polyvinyl chloride resin modification of claim 1, it is characterized in that the initiator that letex polymerization is adopted is any one that chooses from persulphate, organo-peroxide, azo compound, or any one the redox initiator system formed that from sulphite, hydrosulphite, thiosulphate, chooses, consumption is the 0.001-1% of comonomer weight.
5. according to the styrene-acrylonitrile copolymer that is used for ABS and polyvinyl chloride resin modification of claim 1, it is characterized in that the molecular weight regulator that letex polymerization is adopted is the alkyl sulfhydryl of C4-C20, consumption is (0-0.5%) of comonomer weight.
6. according to the styrene-acrylonitrile copolymer that is used for ABS and polyvinyl chloride resin modification of claim 1, it is characterized in that in the described comonomer that vinylbenzene is 65-85%, vinyl cyanide is 15-35%.
7. according to the styrene-acrylonitrile copolymer that is used for ABS and polyvinyl chloride resin modification of claim 1, it is characterized in that in the described comonomer that vinylbenzene is 65-75%, vinyl cyanide is 25-35%.
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| CN2009100189718A CN101659723B (en) | 2009-09-22 | 2009-09-22 | Styrene-acryonitrile copolymer for modifying ABS and PVC resins |
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| CN2009100189718A CN101659723B (en) | 2009-09-22 | 2009-09-22 | Styrene-acryonitrile copolymer for modifying ABS and PVC resins |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103387718A (en) * | 2012-05-08 | 2013-11-13 | 合肥杰事杰新材料股份有限公司 | PVC/ABS alloy and preparation method thereof |
| WO2014019109A1 (en) * | 2012-08-02 | 2014-02-06 | Tian Yuenan | Processing modifier used for polyvinyl chloride pipe and pipe fitting |
| CN104080846A (en) * | 2012-01-17 | 2014-10-01 | 日本A&L株式会社 | Rubber-reinforced styrene resin composition for resin foams, and resin foam |
| CN106084111A (en) * | 2016-07-28 | 2016-11-09 | 淄博华星助剂有限公司 | The preparation method of Ultra-low molecular weight AS resin |
| CN110951193A (en) * | 2019-12-20 | 2020-04-03 | 山东汇丰新材料科技股份有限公司 | Low-density UV special plate and preparation method thereof |
| CN113307903A (en) * | 2021-07-07 | 2021-08-27 | 邢台学院 | Poly (styrene-acrylonitrile) copolymer microsphere and preparation method thereof |
-
2009
- 2009-09-22 CN CN2009100189718A patent/CN101659723B/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104080846A (en) * | 2012-01-17 | 2014-10-01 | 日本A&L株式会社 | Rubber-reinforced styrene resin composition for resin foams, and resin foam |
| CN103387718A (en) * | 2012-05-08 | 2013-11-13 | 合肥杰事杰新材料股份有限公司 | PVC/ABS alloy and preparation method thereof |
| WO2014019109A1 (en) * | 2012-08-02 | 2014-02-06 | Tian Yuenan | Processing modifier used for polyvinyl chloride pipe and pipe fitting |
| CN106084111A (en) * | 2016-07-28 | 2016-11-09 | 淄博华星助剂有限公司 | The preparation method of Ultra-low molecular weight AS resin |
| CN106084111B (en) * | 2016-07-28 | 2018-03-27 | 淄博华星助剂有限公司 | The preparation method of Ultra-low molecular weight AS resins |
| CN110951193A (en) * | 2019-12-20 | 2020-04-03 | 山东汇丰新材料科技股份有限公司 | Low-density UV special plate and preparation method thereof |
| CN113307903A (en) * | 2021-07-07 | 2021-08-27 | 邢台学院 | Poly (styrene-acrylonitrile) copolymer microsphere and preparation method thereof |
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