CN1648164A - High toughness polyburylene terephthalate blend material and its preparing method - Google Patents
High toughness polyburylene terephthalate blend material and its preparing method Download PDFInfo
- Publication number
- CN1648164A CN1648164A CN 200410011396 CN200410011396A CN1648164A CN 1648164 A CN1648164 A CN 1648164A CN 200410011396 CN200410011396 CN 200410011396 CN 200410011396 A CN200410011396 A CN 200410011396A CN 1648164 A CN1648164 A CN 1648164A
- Authority
- CN
- China
- Prior art keywords
- weight
- accounts
- polybutylene terephthalate
- monomer
- nucleocapsid structure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of high toughness polybutylene terephthalate (PBT) blend material and its preparation process. The blend material consists of PBT 70-90 wt% and anti-shock modifier 10-30 wt%. The present invention adopts epoxy functional anti-shock modifier in core-shell structure with butadiene polymer as core in 60 wt% and the copolymer of styrene, acrylonitrile and epoxy propyl methacrylate as shell in 40 wt%. The epoxy functional anti-shock modifier prepared through emulsion grafting polymerization process can toughen PBT well. When the anti-shock modifier accounts for 30 wt%, the blend material has shock strength up to 860 J/m, 20 times higher than pure PBT.
Description
Technical field
The present invention relates to polymeric material field, particularly a kind of high tenacity polybutylene terephthalate intermingling material and preparation method thereof.
Background technology
Polybutylene terephthalate has good physicals and good moulding processability, is widely used in fields such as electronic apparatus, automobile.But the polybutylene terephthalate notch sensitivity is big, and notched Izod impact strength is low, has limited its use range, and the shock resistance of therefore improving polybutylene terephthalate is an extremely significant job.
In recent years, the research of polybutylene terephthalate toughening modifying has a lot, U.S. Pat 4,965, and 111 disclose the toughness reinforcing polybutylene terephthalate of terpolymer EP rubber (EPDM) with the glytidyl methacrylate graft modification; U.S. Pat 4,931,502 disclose with phenylethylene/maleic anhydride copolymer, the toughening agent modified polybutylene terephthalate of nucleocapsid structure.
We can see in the technology that formerly has, for the toughness reinforcing polybutylene terephthalate of polyolefins properties-correcting agent, in order to guarantee the good distribution of properties-correcting agent in polybutylene terephthalate, usually need carry out it functionalized, in the grafting can with the active group of polyester functional group reactions, but the dispersion size of properties-correcting agent in polybutylene terephthalate can not accurately be controlled; For nucleocapsid structure properties-correcting agent, have the controlled characteristics of grain size, but often modified effect is also undesirable with itself and the direct blend of body material, there is the accumulative problem equally in the properties-correcting agent particle.Therefore, also need in co-mixing system, add expanding material usually, improve the dispersion of properties-correcting agent in body material, thereby reach the ideal toughening effect.
Summary of the invention
The object of the invention provides a kind of high tenacity polybutylene terephthalate intermingling material;
Another object of the present invention provides a kind of preparation method of epoxy-functional nucleocapsid structure anti-impact modifier.
Epoxy-functional nucleocapsid structure anti-impact modifier provided by the invention adopts the preparation of emulsion grafting polymerization method.The first step prepares lightly crosslinked polybutadiene rubber and is nuclear; The mix monomer of second step graft phenylethene/vinyl cyanide on polybutadiene rubber nuclear; The 3rd step had the glytidyl methacrylate of reactive behavior in the outermost layer grafting.The epoxy-functional nucleocapsid structure anti-impact modifier of the present invention's preparation, the nuclear phase divinyl accounts for 60% of properties-correcting agent parts by weight, and shell accounts for 40% of properties-correcting agent parts by weight mutually.Styrene/acrylonitrile accounts for the 92-99% of shell phase component parts by weight in the shell phase component, and the ratio of weight and number of styrene/acrylonitrile is 75/25; Glytidyl methacrylate accounts for the 1-8% of shell phase component parts by weight in the shell phase component.
The epoxy-functional nucleocapsid structure anti-impact modifier of the present invention's preparation, its preparation process is as follows:
1) preparation of polyhutadiene emulsion
The 2-4 that removes ionized water and be nuclear monomer weight doubly adds the emulsifying agent rosined soap, accounts for 2.87% of monomer weight; Add the water soluble starter Potassium Persulphate, account for the 0.1-0.5% of monomer weight; Ionogen is a salt of wormwood, and yellow soda ash accounts for 1% of monomer weight; Chain-transfer agent is a lauryl mercaptan, accounts for the 0.1-0.5% of monomer weight.Nitrogen protection is stirred, and polymerization 24h under 55-85 ℃ of condition gets the polyhutadiene emulsion.
2) shell grafted branches polymerization
Shell grafted branches monomer accounts for 40% of properties-correcting agent parts by weight, the mix monomer of the first step graft phenylethene/vinyl cyanide, and the weight ratio of the two is 75/25, styrene/acrylonitrile accounts for the 92-99% of shell monomers weight; Second goes on foot the grafting glytidyl methacrylate, accounts for the 1-8% of shell phase monomer weight.Adopt redox initiation system, the reductive agent ferrous sulfate, help the reductive agent tetrasodium pyrophosphate, glucose, initiator hydrogen phosphide cumene; Nitrogen protection is stirred, and drips monomer under 60-65 ℃ of condition, and reaction times 3-5 hour, add oxidation inhibitor, condense, wash, be drying to obtain epoxy-functional nucleocapsid structure anti-impact modifier after half an hour.
The epoxy-functional nucleocapsid structure anti-impact modifier and the polybutylene terephthalate blend of the present invention's preparation, the polybutylene terephthalate intermingling material of preparation high tenacity.Its preparation process is as follows:
Earlier polybutylene terephthalate and epoxy-functional nucleocapsid structure anti-impact modifier are mixed with high-speed mixer, join then in the twin screw extruder, extrusion temperature is set at 220-230 ℃, and screw slenderness ratio is ф=32.Mixture in twin screw through plasticizing, fusion, compound, extrude, water-cooled, granulation, oven dry, promptly prepare the polybutylene terephthalate intermingling material of high tenacity.The polybutylene terephthalate parts by weight are 70-90% in the intermingling material, and epoxy-functional nucleocapsid structure anti-impact modifier accounts for the 10-30% of matrix material parts by weight.
The polybutylene terephthalate intermingling material of the present invention's preparation is injected into mechanical test standard batten, according to ASTM-D256 canonical measure notched Izod impact strength under 240 ℃ of conditions; According to ASTM-D638 canonical measure tensile strength.Test result shows, when epoxy-functional nucleocapsid structure anti-impact modifier consumption account for the intermingling material weight fraction 30% the time, the notched Izod impact strength of polybutylene terephthalate intermingling material can reach 860J/m, batten is a ductile rupture, and notched Izod impact strength improves about 20 times than pure polybutylene terephthalate; Compare with unmodified nucleocapsid structure properties-correcting agent/polybutylene terephthalate intermingling material simultaneously, tensile strength improves about 1-8Mpa.
The present invention adopts the emulsion grafting polymerization technology, in the preparation process of properties-correcting agent, directly finish the preparation of nucleocapsid structure toughner is functionalized with it, simplified preparation section, save production cost, the epoxy-functional nucleocapsid structure anti-impact modifier of preparing is fit to the toughness reinforcing of polybutylene terephthalate more, prepares high tenacity polybutylene terephthalate intermingling material.
Embodiment:
Embodiment 1
Agitator is being housed, in the 50L high-pressure reactor of condensing works, is feeding nitrogen protection, 55 ℃ of constant temperature.Add deionized water 20kg; Rosined soap 0.287kg; Divinylic monomer 10kg; Potassium Persulphate 0.01kg; Yellow soda ash 0.02kg; Salt of wormwood 0.08kg; Lauryl mercaptan 0.01kg, polymerization 24h under the agitation condition, transformation efficiency is 98%, obtains polybutadiene latex, size of particles is 320nm.
Embodiment 2
Agitator is being housed, in the 50L high-pressure reactor of condensing works, is feeding nitrogen protection, 85 ℃ of constant temperature.Add deionized water 40kg; Rosined soap 0.287kg; Divinylic monomer 10kg; Potassium Persulphate 0.05kg; Yellow soda ash 0.02kg; Salt of wormwood 0.08kg; Lauryl mercaptan 0.05kg, polymerization 24h under the agitation condition, transformation efficiency is 98%, obtains polybutadiene latex, size of particles is 330nm.
Embodiment 3
The PB latex 615g of measuring among the embodiment 1 joins in the reactor; add the 1.5g tetrasodium pyrophosphate; 2.1g glucose; 0.03g ferrous sulfate; deionized water 1000ml; nitrogen protection; 60 ℃ of temperature of reaction, drip styrene/vinyl cyanide in reactor/hydrogen phosphide cumene mix monomer, weight ratio is 180/60/1.14; reaction 3h; add oxidation inhibitor, cohesion behind the 0.5h, washing, drying are not contained the nucleocapsid structure properties-correcting agent of epoxy-functional; example as a comparison, the properties-correcting agent performance is listed in table 1.
Take by weighing 90 parts of polybutylene terephthalates, 10 parts of nucleocapsid structure properties-correcting agent mix in high-speed mixer, join in the twin screw extruder, and extrusion temperature is set at 220-230 ℃.Mixture in twin screw through plasticizing, fusion, compound, extrude, water-cooled, granulation, oven dry, promptly prepare the polybutylene terephthalate intermingling material of high tenacity.The polybutylene terephthalate intermingling material of preparation is injected into mechanical test standard batten, according to ASTM-D256 canonical measure notched Izod impact strength under 240 ℃ of conditions; According to ASTM-D638 canonical measure tensile strength.Under similarity condition, preparation polybutylene terephthalate/nucleocapsid structure properties-correcting agent ratio of components is 80/20,70/30 intermingling material, measures its mechanical property, and concrete outcome sees Table 2,3.
Embodiment 4
The PB latex 615g of measuring among the embodiment 1 joins in the reactor; add the 1.5g tetrasodium pyrophosphate; 2.1g glucose; 0.03g ferrous sulfate; deionized water 1000ml; nitrogen protection, 63 ℃ of temperature of reaction, drip styrene/vinyl cyanide in reactor/hydrogen phosphide cumene mix monomer; weight ratio is 175.5/58.5/1.11; after being added dropwise to complete, begin to drip glytidyl methacrylate/hydrogen phosphide cumene mix monomer, weight ratio is 6/0.03; after finishing, reaction adds oxidation inhibitor; 0.5h back cohesion; washing; drying obtains containing the glytidyl methacrylate parts by weight and is 1% nucleocapsid structure anti-impact modifier, and the properties-correcting agent performance is listed in table 1.
Take by weighing 90 parts of polybutylene terephthalates, 10 parts of epoxy-functional nucleocapsid structure properties-correcting agent mix in high-speed mixer, join in the twin screw extruder, and extrusion temperature is set at 220-230 ℃.Mixture in twin screw through plasticizing, fusion, compound, extrude, water-cooled, granulation, oven dry, promptly prepare the polybutylene terephthalate intermingling material of high tenacity.The polybutylene terephthalate intermingling material of preparation is injected into mechanical test standard batten, according to ASTM-D256 canonical measure notched Izod impact strength under 240 ℃ of conditions; According to ASTM-D638 canonical measure tensile strength.Under similarity condition, preparation polybutylene terephthalate/nucleocapsid structure properties-correcting agent ratio of components is 80/20,70/30 intermingling material, measures its mechanical property, and concrete outcome sees Table 2,3.
Embodiment 5
The PB latex 615g of measuring among the embodiment 1 joins in the reactor; add the 1.5g tetrasodium pyrophosphate; 2.1g glucose; 0.03g ferrous sulfate; deionized water 1000ml; nitrogen protection, 65 ℃ of temperature of reaction, drip styrene/vinyl cyanide in reactor/hydrogen phosphide cumene mix monomer; weight ratio is 166.5/55.5/1.055; after being added dropwise to complete, begin to drip glytidyl methacrylate/hydrogen phosphide cumene mix monomer, weight ratio is 18/0.085; after finishing, reaction adds oxidation inhibitor; 0.5h back cohesion; washing; drying obtains containing the glytidyl methacrylate parts by weight and is 3% nucleocapsid structure anti-impact modifier, and the properties-correcting agent performance is listed in table 1.
Take by weighing 90 parts of polybutylene terephthalates, 10 parts of epoxy-functional nucleocapsid structure properties-correcting agent mix in high-speed mixer, join in the twin screw extruder, and extrusion temperature is set at 220-230 ℃.Mixture in twin screw through plasticizing, fusion, compound, extrude, water-cooled, granulation, oven dry, promptly prepare the polybutylene terephthalate intermingling material of high tenacity.The polybutylene terephthalate intermingling material of preparation is injected into mechanical test standard batten, according to ASTM-D256 canonical measure notched Izod impact strength under 240 ℃ of conditions; According to ASTM-D638 canonical measure tensile strength.Under similarity condition, preparation polybutylene terephthalate/nucleocapsid structure properties-correcting agent ratio of components is 80/20,70/30 intermingling material, measures its mechanical property, and concrete outcome sees Table 2,3.
Embodiment 6
The PB latex 615g of measuring among the embodiment 2 joins in the reactor; add the 1.5g tetrasodium pyrophosphate; 2.1g glucose; 0.03g ferrous sulfate; deionized water 1000ml; nitrogen protection, 65 ℃ of temperature of reaction, drip styrene/vinyl cyanide in reactor/hydrogen phosphide cumene mix monomer; weight ratio is 157.5/52.5/1; after being added dropwise to complete, drip glytidyl methacrylate/hydrogen phosphide cumene mix monomer, weight ratio 30/0.14; after finishing, reaction adds oxidation inhibitor; 0.5h back cohesion; washing; drying obtains containing the nucleocapsid structure anti-impact modifier of glytidyl methacrylate parts by weight 5%, and the properties-correcting agent performance is listed in table 1.
Take by weighing 90 parts of polybutylene terephthalates, 10 parts of epoxy-functional nucleocapsid structure properties-correcting agent mix in high-speed mixer, join in the twin screw extruder, and extrusion temperature is set at 220-230 ℃.Mixture in twin screw through plasticizing, fusion, compound, extrude, water-cooled, granulation, oven dry, promptly prepare the polybutylene terephthalate intermingling material of high tenacity.The polybutylene terephthalate intermingling material of preparation is injected into mechanical test standard batten, according to ASTM-D256 canonical measure notched Izod impact strength under 240 ℃ of conditions; According to ASTM-D638 canonical measure tensile strength.Under similarity condition, preparation polybutylene terephthalate/nucleocapsid structure properties-correcting agent ratio of components is 80/20,70/30 intermingling material, measures its mechanical property, and concrete outcome is listed in table 2,3.
Embodiment 7
The PB latex 615g of measuring among the embodiment 2 joins in the reactor; add the 1.5g tetrasodium pyrophosphate; 2.1g glucose; 0.03g ferrous sulfate; deionized water 1000ml; nitrogen protection, 65 ℃ of temperature of reaction, drip styrene/vinyl cyanide in reactor/hydrogen phosphide cumene mix monomer; weight ratio is 144/48/0.91; after being added dropwise to complete, begin to drip glytidyl methacrylate/hydrogen phosphide cumene mix monomer, weight ratio is 48/0.23; after finishing, reaction adds oxidation inhibitor; 0.5h back cohesion; washing; drying obtains containing the glytidyl methacrylate parts by weight and is 8% nucleocapsid structure anti-impact modifier, and the properties-correcting agent performance is listed in table 1.
Take by weighing 90 parts of polybutylene terephthalates, 10 parts of epoxy-functional nucleocapsid structure properties-correcting agent mix in high-speed mixer, add in the twin screw extruder, and extrusion temperature is set at 220-230 ℃.Mixture plasticizing in twin screw, fusion, compound, extrude, water-cooled, granulation, oven dry, prepare high tenacity polybutylene terephthalate intermingling material.The polybutylene terephthalate intermingling material of preparation is injected into mechanical test standard batten, according to ASTM-D256 canonical measure notched Izod impact strength under 240 ℃ of conditions; According to ASTM-D638 canonical measure tensile strength.Under similarity condition, preparation polybutylene terephthalate/nucleocapsid structure properties-correcting agent ratio of components is 80/20,70/30 intermingling material, measures its mechanical property, and concrete outcome is listed in table 2,3.
Table 1 nucleocapsid structure anti-impact modifier performance
PB content St/AN content grain size
Embodiment GMA content (%)
(％) (％) (μm)
Embodiment 3 60 40 0 0.37
Embodiment 4 60 39 1 0.40
Embodiment 5 60 37 3 0.41
Embodiment 6 60 35 5 0.43
Embodiment 7 60 32 8 0.42
Table 2 polybutylene terephthalate intermingling material notched Izod impact strength
Notched Izod impact strength (J/m)
Embodiment
Ratio of components 90/10 ratio of components 80/20 ratio of components 70/30
Embodiment 3 100 125 146
Embodiment 4 112 617 862
Embodiment 5 132 374 790
Embodiment 6 127 160 760
Embodiment 7 129 150 616
Table 3 polybutylene terephthalate intermingling material tensile strength
Tensile strength (MPa)
Embodiment
Ratio of components 90/10 ratio of components 80/20 ratio of components 70/30
Embodiment 3 42.5 38.8 32.3
Embodiment 4 45.5 39.7 33.2
Embodiment 5 43.6 39.4 34.8
Embodiment 6 44.8 38.5 35.1
Embodiment 7 42.2 40.6 40.7
Claims (3)
1. high-ductility polybutylene terephthalate intermingling material, this intermingling material comprises: polybutylene terephthalate 70-90 weight part, epoxy-functional nucleocapsid structure anti-impact modifier 10-30 weight part.
2. as high-ductility polybutylene terephthalate intermingling material as described in the right 1, it is characterized in that described anti-impact modifier is the nucleocapsid structure toughner of epoxy-functional, nuclear accounts for 60% of toughner weight fraction for polyhutadiene, the shell plastic fraction is a vinylbenzene, vinyl cyanide, the glytidyl methacrylate multipolymer accounts for 40% of properties-correcting agent parts by weight.
3. method for preparing right 1 described epoxy-functional nucleocapsid structure anti-impact modifier, preparation process is as follows:
1) preparation of polyhutadiene emulsion
The 2-4 that removes ionized water and be the nuclear monomer weight ratio doubly adds the emulsifying agent rosined soap, accounts for 2.87% of monomer weight; Add the water soluble starter Potassium Persulphate, account for the 0.1-0.5% of monomer weight; Ionogen is a salt of wormwood, and yellow soda ash accounts for 1% of monomer weight; Chain-transfer agent is a lauryl mercaptan, accounts for the 0.1-0.5% of monomer weight, and nitrogen protection is stirred, and polymerization 24h under 55-85 ℃ of condition gets the polyhutadiene emulsion;
2) shell grafted branches polymerization
The mix monomer of the first step graft phenylethene/vinyl cyanide, the weight ratio of the two are 75/25, and styrene/acrylonitrile accounts for the 92-99% of shell monomers weight; The second step grafting glytidyl methacrylate accounts for the 1-8% of shell phase monomer weight, adopts redox initiation system, the reductive agent ferrous sulfate, helps the reductive agent tetrasodium pyrophosphate, glucose, initiator hydrogen phosphide cumene; Nitrogen protection is stirred, and drips monomer under 60-65 ℃ of condition, and reaction times 3-5 hour, add oxidation inhibitor, condense, wash, be drying to obtain epoxy-functional nucleocapsid structure anti-impact modifier after half an hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410011396 CN1648164A (en) | 2004-12-28 | 2004-12-28 | High toughness polyburylene terephthalate blend material and its preparing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410011396 CN1648164A (en) | 2004-12-28 | 2004-12-28 | High toughness polyburylene terephthalate blend material and its preparing method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1648164A true CN1648164A (en) | 2005-08-03 |
Family
ID=34867760
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410011396 Pending CN1648164A (en) | 2004-12-28 | 2004-12-28 | High toughness polyburylene terephthalate blend material and its preparing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1648164A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102351977A (en) * | 2011-07-15 | 2012-02-15 | 河北工业大学 | Method for preparing acrylate copolymer emulsion used for toughening and modifying polybutylene terephthalate |
| CN103059534A (en) * | 2011-10-20 | 2013-04-24 | 黑龙江鑫达企业集团有限公司 | Polycarbonate blending material with high toughness and preparation method thereof |
| CN106633686A (en) * | 2016-10-21 | 2017-05-10 | 长春工业大学 | Core-shell particle toughened PBT/PC alloy and preparation method |
| CN109679168A (en) * | 2019-01-10 | 2019-04-26 | 骆玲 | A kind of chemical pump nitrile rubber sealing element |
| CN113105729A (en) * | 2020-01-09 | 2021-07-13 | 万华化学集团股份有限公司 | Polylactic resin and preparation method and application thereof |
| CN115678250A (en) * | 2022-10-17 | 2023-02-03 | 浙江红蜻蜓鞋业股份有限公司 | Anti-skid wear-resistant sole and processing technology thereof |
-
2004
- 2004-12-28 CN CN 200410011396 patent/CN1648164A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102351977A (en) * | 2011-07-15 | 2012-02-15 | 河北工业大学 | Method for preparing acrylate copolymer emulsion used for toughening and modifying polybutylene terephthalate |
| CN102351977B (en) * | 2011-07-15 | 2013-04-17 | 河北工业大学 | Method for preparing acrylate copolymer emulsion used for toughening and modifying polybutylene terephthalate |
| CN103059534A (en) * | 2011-10-20 | 2013-04-24 | 黑龙江鑫达企业集团有限公司 | Polycarbonate blending material with high toughness and preparation method thereof |
| CN106633686A (en) * | 2016-10-21 | 2017-05-10 | 长春工业大学 | Core-shell particle toughened PBT/PC alloy and preparation method |
| CN109679168A (en) * | 2019-01-10 | 2019-04-26 | 骆玲 | A kind of chemical pump nitrile rubber sealing element |
| CN113105729A (en) * | 2020-01-09 | 2021-07-13 | 万华化学集团股份有限公司 | Polylactic resin and preparation method and application thereof |
| CN113105729B (en) * | 2020-01-09 | 2022-08-05 | 万华化学集团股份有限公司 | Polylactic resin and preparation method and application thereof |
| CN115678250A (en) * | 2022-10-17 | 2023-02-03 | 浙江红蜻蜓鞋业股份有限公司 | Anti-skid wear-resistant sole and processing technology thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1160406C (en) | A polymethylmethacrylate resin with an impact modifier capsulated therein and a process of preparing for the same | |
| CN101654501B (en) | Methacryl resin composition having excellent impact strength and transmittancy | |
| CN1944525A (en) | Method for preparing graft rubber latex having low residual monomer content | |
| CN1884326A (en) | Porous polypropylene particle suspension solid phase graft-modification method | |
| CN1415661A (en) | Cross blend material based on polycarbonate and its prepn. method | |
| CN1648164A (en) | High toughness polyburylene terephthalate blend material and its preparing method | |
| CN1348482A (en) | Processing aid for thermoplastic resin and thermoplastic resin composition containing the same | |
| CN106633686A (en) | Core-shell particle toughened PBT/PC alloy and preparation method | |
| CN1211406C (en) | Emulsion polymerized polyacrylate rubber, impact modifiers and blends obtained therefrom, and method for making | |
| CN1163535C (en) | Impact modifiers for thermoplastic resins | |
| JP3396240B2 (en) | Methacrylic resin composition | |
| CN1205240C (en) | Thermoplastic resin and preparation method thereof | |
| CN1257937C (en) | Thermoplastic resin compsn. having excellent chemical resistance and easy vacuum formability | |
| CN1266214C (en) | Modifier for increasing impact resistance of polyvinyl chloride | |
| CN1476470A (en) | Thermoplastic resin composition with excellent impact resistance | |
| CN1197889C (en) | Transparent impact-resistant thermoplastic resin composition | |
| CN1488657A (en) | Nucleocapside structure PVC impact resistance modifier, and preparing method and use thereof | |
| CN103897110B (en) | Styrene resin blend with weather resistance and preparation method thereof | |
| CN1114635C (en) | Synthesis of transparnt shock-resisting modifier | |
| CN1587290A (en) | Process for preparing acrylonitrile-chlorinated polyethylene styrene resin copolymer | |
| CN1313535C (en) | Thickener for thermoplastic polyester resin, thermoplastic polyester resin composition containing the same, and molded object obtained therefrom | |
| CN1357557A (en) | Production process of impact-resisting and heat resistant copolymerized resin | |
| CN1126765C (en) | Process for synthesizing anti-lash modifying agent used for polyvinyl-chloride resin | |
| CN106893246A (en) | Preparation method of ABS resin | |
| CN1211431C (en) | Thermoplastic resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |