CN1145662C - Cross-linked powdered rubber and its preparing process and usage - Google Patents
Cross-linked powdered rubber and its preparing process and usage Download PDFInfo
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- CN1145662C CN1145662C CNB001303864A CN00130386A CN1145662C CN 1145662 C CN1145662 C CN 1145662C CN B001303864 A CNB001303864 A CN B001303864A CN 00130386 A CN00130386 A CN 00130386A CN 1145662 C CN1145662 C CN 1145662C
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- 239000004033 plastic Substances 0.000 claims abstract description 26
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- 238000002360 preparation method Methods 0.000 claims abstract description 16
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- 230000000052 comparative effect Effects 0.000 description 10
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- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 5
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Abstract
The present invention provides crosslinking powdered rubber with the grain diameter of 50 to 300 nm and a preparation method and the usage thereof. The crosslinking powdered rubber is prepared from various crosslinking synthetic rubber emulsions as raw materials through drying. The crosslinking powdered rubber can be combined with various plastics, is extremely easy to disperse in a plastic parent body and is manufactured into various toughening plastics and fully sulfurized thermoplastic elastic bodies.
Description
The present invention relates to powdered rubber, more particularly, the present invention relates to the powdered rubber of cross-linking type and the Preparation method and use of this powdered rubber.
Powdered rubber is meant pulverous natural rubber and synthetic rubber.Powdered rubber and bulk or sheet rubber phase ratio, just change has taken place in its physical aspect, does not change its basic chemical property.From the development original intention of powdered rubber, people wish to utilize its advantage aspect processing replacing traditional rubber processing aspect the production rubber item, thereby cut down finished cost, and improve working strength of workers and operating environment.Can be for various reasons, the tempo of producing rubber item with powdered rubber is slow, the result of the traditional rubber processing of large-scale replacement that people do not occur at all and estimated.
Because to some inherent understanding of the purposes of powdered rubber, people obtain powdered rubber and often wish that it is not crosslinked, otherwise will be unfavorable for further being processed into rubber item.Thereby seldom about the research and development of cross-linked powdered rubber.If but consider that from the another one angle though crosslinked powdered rubber is unfavorable for the processing rubber goods, but it is used as plastics toughening agent or develops new product, and as novel fully sulfurized thermoplastic elastomer aspect special advantages is arranged.Crosslinked powdered rubber is because the macromolecular chain of rubber is crosslinked a constraint, and after reaching certain high crosslinking degree, its particle is substantially no longer adhered to one another because of the external force effect, thereby can keep its initial size.Thereby in plastic toughening was used, it was toughness reinforcing to select for use the powdered rubber of the cross-linking type of suitable kind, suitable particle size range according to required toughness reinforcing plastics, to reach optimum toughening effect.Equally in preparation blend type fully sulfurized thermoplastic elastomer process, because rubber particles self-crosslinking, can not be linked to be reticulated structure mutually, thereby can obtain " island " type structure of plastic wraps rubber particles at an easy rate, thereby guaranteed that prepared thermoplastic elastomer has comparatively ideal mechanical property.
At present, though existing all kinds of powdered rubber commodity sellings, the particle diameter of powder is all bigger, and WidmerH is at RubberAge, and 1974,106 (11): 41 article middle fingers go out the general particle diameter of powdered rubber of industrial application below 1mm, but can be very thinless.Because particle diameter is high and the operation dust is big less than the powder of 0.5mm pre-mixing energy consumption when the processing rubber goods, finally can cause the discrete and layering of sizing material.For the powder nbr rubber of the cross-linking type that uses as plastics additive, its particle diameter is also in the millimeter level.Yet the preparation of plastic toughening and novel fully sulfurized thermoplastic elastomer all needs thinner rubber particle (micron is following at least) to come and plastic blend, could guarantee that like this interface bonding is good between two-phase, the stress defective do not occur.
Expecting very thin cross-linked powdered rubber, is that feedstock production is more satisfactory with the rubber latex.The inventor has applied for Chinese patent 99125530.5 on December 3rd, 1999: " full vulcanized powdered rubber with controllable particle diameter and method for making thereof and purposes ".In this patent, fully vulcanized powder rubber is to be raw material with the rubber latex, adds or do not add crosslinking coagent, through cross-linking radiation rubber size is fixed, and obtains fully vulcanized powder rubber through precipitation or spray drying process then.
The inventor discovers have some rubber latexs between the rubber molecule certain cross can take place in the synthetic process, thereby make resulting rubber latex have certain crosslinking degree by experiment.We are referred to as the crosslinking-type rubber emulsion.For this crosslinking-type rubber emulsion, when the crosslinking degree of himself was higher, need not further cross-linking radiation can the spray-dried powdered rubber that makes.Certainly the crosslinking degree of this powdered rubber will be lower than the fully vulcanized powder rubber that obtains through irradiation for rubber of the same race, and we are referred to as cross-linked powdered rubber.This cross-linked powdered rubber can be used for the preparation of plastic toughening and thermoplastic elastomer.And owing to do not need radiation vulcanization, its cost will be lower than fully vulcanized powder rubber.
Therefore it is thinner to the purpose of this invention is to provide a kind of particle diameter, and what need not to use separant is the powdered rubber of free flowable cross-linking type.
Another object of the present invention provides the preparation method of described cross-linked powdered rubber.
The present invention also has a purpose to provide the application of described cross-linked powdered rubber in preparation toughened plastics and fully sulfurized thermoplastic elastomer.
Cross-linked powdered rubber of the present invention be a kind of be raw material with the cross-linking type synthetic rubber latex, the powdered rubber that drying obtains.The gel content of described cross-linked powdered rubber and swelling index and be consistent as the gel content and the swelling index of the cross-linking type synthetic rubber latex of raw material, its gel content is 80% weight or higher, is preferably 85% weight or higher.Adopt swelling index to represent its crosslinking degree, its swelling index is not more than 15.Cross-linked powdered rubber of the present invention need not add separant and get final product unrestricted flow.Certainly if desired, also can add separant in the cross-linked powdered rubber of the present invention, with its flowable of further raising and resistance to blocking.
Cross-linked powdered rubber of the present invention has smaller particle size, average out to 50～300nm.
Each particulate in the cross-linked powdered rubber of the present invention all is a homogeneous, and promptly single particulate all is a homogeneous on forming, and particulate inside is not found layering, divided equal uneven phase phenomenon under the observation of existing microtechnique.
To the kind of cross-linked powdered rubber of the present invention without any restriction, it can be the cross-linked powdered rubber that adopts the synthetic rubber latex of various cross-linking types to make, for example cross-linked powdery styrene-butadiene rubber(SBR), cross-linked powdery carboxylic styrene-butadiene rubber, cross-linked powdery polybutadiene rubber, cross-linked powdery acrylonitrile butadiene, cross-linked powdery carboxy nitrile rubber, cross-linked powdery chloroprene rubber, cross-linked powdery acrylic elastomer etc.
The preparation method of cross-linked powdered rubber of the present invention is:
Synthetic rubber latex with various cross-linking types is a raw material, and drying can obtain cross-linked powdered rubber.Drying process can or precipitate desiccating method, preferably spray drying method with spray-drying process.If the spray-drying process of using, the inlet temperature of spray-dryer can be controlled in 100～200 ℃, temperature out is controlled at 20～80 ℃.
When the preparation cross-linked powdered rubber, the kind of used cross-linking type synthetic latex can be the synthetic rubber latex of all kinds of cross-linking types, requires its gel content greater than 80% weight, and more than preferred 85% weight, swelling index is not more than 15.The cross-linking type synthetic latex can be selected from: cross-linking type butylbenzene rubber latex, cross-linking type carboxylic styrene-butadiene rubber emulsion, cross-linking type polybutadiene rubber emulsion, cross-linking type acrylonitrile-butadiene rubber latex, cross-linking type carboxy nitrile rubber emulsion, cross-linking type neoprene latex, crosslinking acrylate rubber latex.
Cross-linked powdered rubber of the present invention can be used for the preparation of plastic toughening and fully sulfurized thermoplastic elastomer.Basic preparation method be with cross-linked powdered rubber of the present invention and plastics by a certain percentage mixing on the rubber plastic blend equipment of routine and under the processing condition of routine, if desired, add various processing aids in right amount.
Aspect plastic toughening, the weight ratio of powdered rubber and plastics is 0.5: 99.5～50: 50, is preferably 5: 95～30: 70.By toughness reinforcing plastics can be polymeric amide, polypropylene, polyethylene, polyvinyl chloride, urethane, Resins, epoxy, polyester, polycarbonate, polyoxymethylene, polystyrene, polyphenylene oxide, polyphenylene sulfide, polyimide, polysulfones and multipolymer or blend etc.
Aspect the preparation fully sulfurized thermoplastic elastomer, the weight ratio of powdered rubber and plastics is 30: 70～75: 25, is preferably 50: 50～70: 30.Employed plastics can be polymeric amide, polypropylene, polyethylene, polyvinyl chloride, urethane, Resins, epoxy, polyester, polycarbonate, polyoxymethylene, polystyrene, polyphenylene oxide, polyphenylene sulfide, polyimide, polysulfones and multipolymer or blend etc.
Cross-linked powdered rubber of the present invention, particle diameter is little and even.Its preparation method is compared with fully vulcanized powder rubber, does not need the irradiation process, and cost is lower, and the preparation method is simpler, convenient.
Further describe the present invention below in conjunction with embodiment, scope of the present invention is not subjected to the restriction of these embodiment.Scope of the present invention proposes in claims.
Accompanying drawing 1 is the stereoscan photograph of gained cross-linked powdery styrene-butadiene rubber(SBR) among the embodiment 1.
In following examples, gel content is measured in accordance with the following methods:
Accurately take by weighing the about 0.1g of cross-linked powdered rubber that spraying drying obtains, wrap with general lens paper, wrap into again in the 200 purpose copper mesh, accurately weighing, then it is boiled in toluene, quality substantially constant after thorough drying is as the criterion boiling time with copper mesh and wrap, generally is about 6 hours.Copper mesh that will fully boil and wrap complete drying thereof afterwards, accurately weighing.According to following formula calculated for gel content:
Gel content (%)=[W
0-(W
1-W
2)]/W
0* 100%
In the formula: W
0Be the powdered rubber example weight;
W
1Weight for copper mesh before boiling and wrap thereof;
W
2After boiling, the copper mesh after thorough drying and the weight of wrap thereof.
Swelling index is measured in accordance with the following methods:
With crosslinking-type rubber emulsion drying and forming-film (can directly use dry good powder) as the film forming difficulty.(copper mesh weight is W to the capsule that 200 order copper mesh are made
0) steep in the toluene, place a little, pulling out then weighs rapidly is designated as W
1The film (or powder) that takes by weighing about 0.1g is put into the copper mesh capsule, and film and copper mesh one foaming are gone in the toluene, is positioned over shady and cool place swelling after 24 hours, copper mesh is carefully pulled out together with the good gel of swelling, inhale fast and remove the solvent of gel surface, weigh rapidly then, weight is designated as W
2Copper mesh after weighing and gel finish-drying to weight are no longer changed, and weighing is designated as W
3Swelling index is calculated by following formula:
Swelling index=(W
2-W
1)/(W
3-W
0)
Embodiment 1.
Solid content is commercially available styrene-butadiene latex (Lanhua Latex Research and Development Centre's production of 45 weight %, the trade mark: butylbenzene-50), by the spray-dryer spraying drying, the inlet temperature of spray-dryer is 140 ℃～160 ℃, and temperature out is 40 ℃～60 ℃, collects dried butylbenzene powdered rubber in cyclonic separator, obtain cross-linking type butylbenzene powdered rubber sample 1, its particle diameter is about 100nm, and gel content is 88.9%, and swelling index is 12.7.
Embodiment 2.
Solid content is that (Ji is combined to resin processing plant to be produced for the commercially available polybutadiene latex of 40 weight %, the trade mark: 0700), by the spray-dryer spraying drying, the inlet temperature of spray-dryer is 140 ℃～160 ℃, temperature out is 40 ℃～60 ℃, collect dried powdered rubber in cyclonic separator, obtain cross-linking type polyhutadiene powdered rubber sample 2, its particle diameter is about 280nm.Gel content is 84.6%, and swelling index is 13.3.
Embodiment 3
With cross-linking type butylbenzene powdered rubber sample 1 (embodiment 1) and polypropylene powder (Tianjin second petrochemical plant, the trade mark is the 3-1 type) and antioxidant 1010 (Switzerland vapour Ba Jiaji production) mixing, sample 1 is 10/90 with polyacrylic weight ratio, and the oxidation inhibitor consumption accounts for 0.5% of powdered rubber and plastics gross weight.Adopt the ZSK-25 twin screw extruder blend granulation of German WP company, each section of forcing machine temperature is respectively: 170 ℃, 185 ℃, 190 ℃, 190 ℃, 190 ℃ and 190 ℃ (head temperature).Pellet is made the standard batten through injection moulding, carries out every Mechanics Performance Testing, and testing standard and result are as shown in table 1.
Comparative example 1
Polypropylene powder among the embodiment 1, oxidation inhibitor directly mixed after the twin screw extruder granulation, all the other conditions are identical with embodiment 1.Mechanical test results is listed in table 1.
Embodiment 4
With transparent polystyrene pellet (Yanshan Petrochemical production, trade mark 666D) and cross-linking type butylbenzene powdered rubber sample 1 (embodiment 1) and antioxidant 1010 (Switzerland vapour Ba Jiaji production) mix.The weight ratio of cross-linking type butylbenzene powdered rubber and polystyrene is 15: 85, and the oxidation inhibitor consumption accounts for 0.5% of powdered rubber and plastics gross weight.Adopt the ZSK-25 twin screw extruder blend granulation of German WP company, each section of forcing machine temperature is respectively: 170 ℃, 180 ℃, 180 ℃, 180 ℃, 180 ℃ and 180 ℃ (head temperature).Pellet is made the standard batten through injection moulding, carries out every Mechanics Performance Testing, and its result is as shown in table 1.
Comparative example 2
Polystyrene pellet among the embodiment 4 is directly made the standard batten through injection moulding, carry out every Mechanics Performance Testing, the results are shown in table 1.
Comparative example 3
Cross-linking type butylbenzene powdered rubber among the embodiment 4 is all used (the Yanshan Petrochemical production of SBS thermoplastic elastomer, the trade mark 1401) substitutes, the weight ratio of SBS thermoplastic elastomer and polystyrene is 15: 85, and all the other conditions are identical with embodiment 4, and Mechanical test results is listed in table 1.
Embodiment 5
With polypropylene granules (Jinan Refinery production, trade mark T30S) and cross-linking type polyhutadiene powdered rubber sample 2 (embodiment 2) and antioxidant 1010 (Switzerland vapour Ba Jiaji production) mix, specifically consist of: cross-linking type polyhutadiene powdered rubber and polyacrylic weight ratio are 10: 90, and the oxidation inhibitor consumption accounts for 0.5% of powdered rubber and plastics gross weight.Adopt the ZSK-25 twin screw extruder blend granulation of German WP company, each section of forcing machine temperature is respectively: 170 ℃, 185 ℃, 190 ℃, 190 ℃, 190 ℃ and 190 ℃ (head temperature).Pellet is made the standard batten through injection moulding, carries out every Mechanics Performance Testing, and its result is as shown in table 1.
Comparative example 4
Polypropylene granules among the embodiment 5 is directly made the standard batten through injection moulding, carry out every Mechanics Performance Testing, the results are shown in table 1.
Comparative example 5
All use terpolymer EP rubber pellet (the Du Pont road produces, the trade mark 3745) to substitute the cross-linking type polyhutadiene powdered rubber among the embodiment 5, specifically consist of: terpolymer EP rubber and polyacrylic weight ratio are 10: 90.All the other conditions are identical with embodiment 1, and Mechanical test results is listed in table 1.
Embodiment 6
With cross-linking type butylbenzene powdered rubber sample 1 (embodiment 1) and polypropylene granules (Yanshan Petrochemical, the trade mark 1300) and antioxidant 1010 (Switzerland vapour Ba Jiaji production) mix, sample 1 is 70/30 with polyacrylic weight ratio, and the oxidation inhibitor consumption accounts for 0.5% of powdered rubber and plastics gross weight.Adopt the ZSK-25 twin screw extruder blend granulation of German WP company, each section of forcing machine temperature is respectively: 170 ℃, 185 ℃, 190 ℃, 190 ℃, 190 ℃ and 190 ℃ (head temperature).Pellet is made the standard batten through injection moulding, carries out every Mechanics Performance Testing, and testing standard and result are as shown in table 2.
Embodiment 7
With cross-linking type butylbenzene powdered rubber sample 1 (embodiment 1) and polypropylene granules (Yanshan Petrochemical, the trade mark 1300) and antioxidant 1010 (Switzerland vapour Ba Jiaji production) mix, sample 1 is 50: 50 with polyacrylic weight ratio, and the oxidation inhibitor consumption accounts for 0.5% of powdered rubber and plastics gross weight.Adopt the ZSK-25 twin screw extruder blend granulation of German WP company, each section of forcing machine temperature is respectively: 170 ℃, 185 ℃, 190 ℃, 190 ℃, 190 ℃ and 190 ℃ (head temperature).Pellet is made the standard batten through injection moulding, carries out every Mechanics Performance Testing, and testing standard and result are as shown in table 2.
Table 1
| Tensile strength | Tension fracture elongation rate | The Izod notched Izod impact strength | Flexural strength | Modulus in flexure | |
| Embodiment 3 | 29.5 | 347 | 102 | 29.6 | 1.33 |
| Comparative example 1 | 36.2 | 313 | 43.7 | 35.9 | 1.63 |
| Embodiment 4 | 35.2 | 32 | 99.5 | 50.9 | 2.36 |
| Comparative example 2 | 51.6 | 6.0 | 31.0 | 83.7 | 3.35 |
| Comparative example 3 | 38.3 | 36 | 47.4 | 53.8 | 2.66 |
| Embodiment 5 | 29.8 | 202 | 90.8 | 31.4 | 1.46 |
| Comparative example 4 | 34.8 | 502 | 46.8 | 34.4 | 1.56 |
| Comparative example 5 | 28.7 | 171 | 70.0 | 29.1 | 1.33 |
| Unit | MPa | ％ | J/m | MPa | GPa |
| Testing standard | GB1040 | GB1040 | GB1843 | GB9341 | GB9341 |
Table 2
| Tensile break strength | Tension fracture elongation rate | Tensile set | 100% tensile modulus | Shore hardness | |
| Embodiment 6 | 11.6 | 130 | 22 | 11.3 | 88(HA) |
| Embodiment 7 | 18.7 | 264 | 126 | 17.2 | 45(HD) |
| Unit | MPa | ％ | ％ | MPa | - |
| Testing standard | ASTM D412 | ASTM D412 | ASTM D412 | ASTM D412 | ASTM D2240- 95 |
Claims (12)
1. cross-linked powdered rubber, the particle diameter that it is characterized in that this cross-linked powdered rubber is 50～300nm, and gel content is not less than 80% weight, and its particulate is a homogeneous.
2. by the described powdered rubber of claim 1, it is characterized in that the gel content of described powdered rubber is not less than 85% weight.
3. by the described powdered rubber of claim 1, it is characterized in that the swelling index of described powdered rubber is not more than 15.
4. press each described powdered rubber of claim 1～3, it is characterized in that described powdered rubber comprises cross-linked powdery styrene-butadiene rubber(SBR), cross-linked powdery carboxylic styrene-butadiene rubber, cross-linked powdery polybutadiene rubber, cross-linked powdery acrylonitrile butadiene, cross-linked powdery carboxy nitrile rubber, cross-linked powdery chloroprene rubber, cross-linked powdery acrylic elastomer.
5. press the preparation method of each described cross-linked powdered rubber of claim 1～4, it is characterized in that with the cross-linking type synthetic rubber latex be raw material, drying obtains cross-linked powdered rubber.
6. by the described method of claim 5, it is characterized in that the gel content of described synthetic rubber latex is not less than 80% weight.
7. by the described method of claim 5, it is characterized in that the gel content of described synthetic rubber latex is not less than 85% weight.
8. by the described method of claim 5, it is characterized in that the swelling index of described synthetic rubber latex is not more than 15.
9. by the described method of claim 5, it is characterized in that described synthetic rubber latex is selected from cross-linking type butylbenzene rubber latex, cross-linking type carboxylic styrene-butadiene rubber emulsion, cross-linking type polybutadiene rubber emulsion, cross-linking type acrylonitrile-butadiene rubber latex, cross-linking type carboxy nitrile rubber emulsion, cross-linking type neoprene latex, crosslinking acrylate rubber latex.
10. by the described method of claim 5, it is characterized in that described drying is to carry out spraying drying or by carrying out with the precipitation desiccating method with spray-dryer.
11. by the described method of claim 10, it is characterized in that when using described spray-dryer to carry out spraying drying, the inlet temperature of spray-dryer is 100～200 ℃, temperature out is 20～80 ℃.
12. be used for the application of toughened plastics or preparation thermoplastic elastomer by each described cross-linked powdered rubber of claim 1～4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001303864A CN1145662C (en) | 2000-11-03 | 2000-11-03 | Cross-linked powdered rubber and its preparing process and usage |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001303864A CN1145662C (en) | 2000-11-03 | 2000-11-03 | Cross-linked powdered rubber and its preparing process and usage |
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| Publication Number | Publication Date |
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| CN1353131A CN1353131A (en) | 2002-06-12 |
| CN1145662C true CN1145662C (en) | 2004-04-14 |
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| CNB001303864A Expired - Lifetime CN1145662C (en) | 2000-11-03 | 2000-11-03 | Cross-linked powdered rubber and its preparing process and usage |
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Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1239587C (en) * | 2003-04-03 | 2006-02-01 | 中国石油化工股份有限公司 | Composite powder, its preparation method and application |
| CN1328352C (en) * | 2004-10-27 | 2007-07-25 | 中国石油化工股份有限公司 | Long persistence luminous polyamide composition and method of making the same |
| CN100348662C (en) * | 2004-10-27 | 2007-11-14 | 中国石油化工股份有限公司 | High-brilliance high-ductility polycarbonate composition and its preparation method |
| CN100491461C (en) * | 2006-01-23 | 2009-05-27 | 中国石油化工股份有限公司 | Toughened polystyrene composition and its preparation method |
| CN102030929B (en) * | 2009-09-25 | 2012-04-18 | 中国石油化工股份有限公司 | Styrene-butadiene vulcanized rubber and preparation method thereof |
| CN102268174B (en) * | 2010-06-04 | 2016-08-17 | 中国石油化工股份有限公司 | A kind of high-fire resistance high-toughness epoxy resin compositions and preparation method thereof |
| CN102453318A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Toughened polylactic resin composition and preparation method thereof |
| CN102453291B (en) * | 2010-10-25 | 2013-11-06 | 中国石油化工股份有限公司 | Anti-impact polyvinyl chloride composition and preparation method thereof |
| CN102453323B (en) * | 2010-10-25 | 2013-06-05 | 中国石油化工股份有限公司 | Organic compound processing aid for polyolefin and alloy thereof and preparation method and application thereof |
| ES2899158T3 (en) | 2011-03-04 | 2022-03-10 | China Petroleum & Chem Corp | Fully vulcanized electrically conductive thermoplastic elastomer and method of preparing same |
| CN102311586B (en) * | 2011-09-26 | 2013-06-19 | 青岛国恩科技股份有限公司 | PP/SBR (polypropylene/styrene butadiene rubber) blended modified composite material and preparation method thereof |
| CN103087438B (en) * | 2011-11-02 | 2015-02-11 | 中国石油化工股份有限公司 | Impact-resistant polyvinyl chloride composition and preparation method thereof |
| CN102786620B (en) * | 2012-07-18 | 2015-07-15 | 杭州蓝诚实业有限公司 | Small-particle-size carboxylic styrene-butadiene latex and its preparation method |
| CN108017744B (en) * | 2016-11-03 | 2021-07-30 | 中国石油化工股份有限公司 | A kind of powder carboxylated styrene-butadiene rubber and its preparation method and application |
| CN109929259B (en) * | 2019-04-17 | 2021-06-04 | 山东显元化工研究院有限公司 | SBR (styrene butadiene rubber) asphalt modifier and preparation method thereof |
| CN110484038A (en) * | 2019-08-12 | 2019-11-22 | 北京东方雨虹防水技术股份有限公司 | A kind of underground engineering polymer spray film water-proofing material and preparation method thereof |
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2000
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