CN115558116B - Preparation method and application of non-precipitation non-sticky organic silicon master batch - Google Patents
Preparation method and application of non-precipitation non-sticky organic silicon master batch Download PDFInfo
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- CN115558116B CN115558116B CN202111559605.0A CN202111559605A CN115558116B CN 115558116 B CN115558116 B CN 115558116B CN 202111559605 A CN202111559605 A CN 202111559605A CN 115558116 B CN115558116 B CN 115558116B
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- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 15
- 239000010703 silicon Substances 0.000 title claims abstract description 15
- 238000001556 precipitation Methods 0.000 title claims abstract description 10
- 150000002978 peroxides Chemical class 0.000 claims abstract description 20
- 239000004033 plastic Substances 0.000 claims abstract description 17
- 229920003023 plastic Polymers 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000000376 reactant Substances 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- 229920001971 elastomer Polymers 0.000 claims description 22
- 239000004743 Polypropylene Substances 0.000 claims description 12
- -1 polypropylene Polymers 0.000 claims description 11
- 229920001296 polysiloxane Polymers 0.000 claims description 11
- 229920000098 polyolefin Polymers 0.000 claims description 10
- 229920001155 polypropylene Polymers 0.000 claims description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 7
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- 229920005604 random copolymer Polymers 0.000 claims description 3
- 230000000740 bleeding effect Effects 0.000 claims description 2
- KVWLLOIEGKLBPA-UHFFFAOYSA-N 3,6,9-triethyl-3,6,9-trimethyl-1,2,4,5,7,8-hexaoxonane Chemical group CCC1(C)OOC(C)(CC)OOC(C)(CC)OO1 KVWLLOIEGKLBPA-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 150000003384 small molecules Chemical group 0.000 abstract description 4
- 229920002379 silicone rubber Polymers 0.000 description 5
- 239000004945 silicone rubber Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention relates to the technical field of C08K9/06, in particular to a preparation method and application of a non-precipitation non-sticky organic silicon master batch, and the preparation method of the non-precipitation non-sticky organic silicon master batch comprises the following steps: mixing the polymerization reactant of the organosilicon master batch and peroxide in an internal mixer at 120-200 ℃, and then extruding and granulating. The organosilicon master batch obtained by the preparation method is not sticky, and the internal mixer grafting reaction process is adopted, so that the master batch has lower small molecule residue and low VOC; the method ensures that the master batch is better and more uniformly dispersed in the modified plastic system, and has smaller influence on the impact performance of the modified plastic.
Description
Technical Field
The invention relates to the technical field of C08K9/06, in particular to a preparation method and application of a non-precipitation non-sticky organic silicon master batch.
Background
The scratch resistance of the traditional organic silicon master batch is required to be improved to a certain extent by applying the organic silicon master batch to the processing of modified plastics, and other series of problems exist, for example, the application of the scratch resistance agent is limited to a certain extent by synthesizing the scratch resistance agent, a toughening agent, talcum powder, a lubricant, a light stabilizer, an antioxidant and the like with polypropylene into a polypropylene material in Chinese patent CN 106243483B, and the VOC content is reduced to a certain extent by using a supercritical fluid in the preparation process, however, the impact performance of the polypropylene material is greatly influenced by the addition of the scratch resistance agent. CN 106147027A a polypropylene masterbatch is obtained by using polypropylene, polysiloxane, long chain alkyl silicone oil and antioxidant, which masterbatch has the problem of bleeding out and sticking after a long time.
Disclosure of Invention
Aiming at some problems existing in the prior art, the first aspect of the invention provides a preparation method of a non-precipitation and non-sticky organic silicon master batch, which comprises the following steps: mixing the polymerization reactant of the organosilicon master batch and peroxide in an internal mixer at 120-200 ℃, and then extruding and granulating.
Preferably, the banburying temperature is 160 ℃.
In the prior art, a compatibilizer is generally used for promoting dispersibility, and the applicant finds that when the weight average molecular weight of the organosilicon raw rubber is 1200000-2000000 in the application, the adhesion phenomenon of the organosilicon master batch obtained by adopting a normal-temperature banburying process needs to be reduced, and surprisingly finds that when the temperature is 120-200 ℃ in banburying, the adhesion phenomenon of the obtained organosilicon master batch is obviously reduced, the viscosity exposure is not increased, and the applicant considers that the possible reason is that the organosilicon raw rubber has larger weight average molecular weight, if the conventional normal-temperature banburying mixing process is adopted, the dispersity of the organosilicon raw rubber and polyolefin can not be effectively improved in the process of repeatedly deforming and recovering deformation of raw materials, and in the banburying process of 120-200 ℃, the contact area of the organosilicon raw rubber and the polyolefin is increased, and meanwhile, the grafting polymerization is completed in the process of repeated deformation and recovery deformation, and the small molecule residue is extremely low and the precipitation rate is low.
In one embodiment, the polymerization reactants of the silicone masterbatch include a silicone raw rubber having a weight average molecular weight of 1200000-2000000 and a polyolefin.
Preferably, the silicone rubber contains vinyl groups.
Preferably, the vinyl content is 0.01 to 0.21mol%, more preferably 0.03 to 0.05mol%.
The organosilicon raw rubber in the application can be obtained by a person skilled in the art according to a conventional preparation method.
Preferably, the weight ratio of the organosilicon raw rubber to the polyolefin is 1: (0.5-2.5), preferably 1: (0.7-2.3), more preferably 1:1.6.
Preferably, the weight ratio of the peroxide to the silicone rubber is (0.01-0.6): 60, preferably 0.3:60.
In one embodiment, the method for preparing the silicone masterbatch comprises: adding the polymerization reactant of the organosilicon master batch and the peroxide into an internal mixer, banburying at 120-200 ℃, and then extruding and granulating, wherein the peroxide is added into the internal mixer for n times, and n is more than or equal to 2.
The applicant adopts the conventional organosilicon master batch on the market to process plastics, discovers that the impact performance of the modified plastics is greatly influenced, the applicant performs unexpected operation in a series of subsequent researches, the peroxide is added into an internal mixer in batches, the obtained organosilicon master batch has almost no influence on the impact performance of the modified plastics, and the unexpected discovery that the impact performance effect is higher by adding organosilicon raw rubber or polyolefin in batches, the applicant considers that possible reasons are that the peroxide is added in batches, at the moment, the long and short chain segments have more balanced grafting reaction, the controllability is high, the internal stress defect of the organosilicon master batch is low, the grafting controllability is low by adopting a mode of adding reactants in batches, the acting force between the reactants is strong, the wettability between the organosilicon and the polyolefin chain segments is poor, and the friction effect between materials is influenced.
Preferably, the peroxide is added to the internal mixer in 3 portions.
Preferably, 3 peroxide feeds into the internal mixer in a weight ratio of 1 (4-6): (1-5), more preferably 1:5:3.
The peroxide is added to the internal mixer for the same time intervals in this application.
In one embodiment, the time for the banburying is 15 to 30min, preferably 20min.
In one embodiment, the granulation temperature is 160-250 ℃, preferably 200 ℃.
In one embodiment, the peroxide is 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane.
In one embodiment, the polyolefin is a random copolymer polypropylene.
Preferably, the random copolymer polypropylene is RANPELEN J-560M, available from korea music.
The second aspect of the invention provides an application of the preparation method of the non-precipitation non-sticky organosilicon master batch in modified plastics.
Preferably, the modified plastic is PP and T20 composite plastic, PP, EPDM and T20 composite plastic.
Compared with the prior art, the invention has the following beneficial effects:
(1) The method adopts banburying grafting technology, and the grafting reaction is completed in the banburying process at the high temperature of 120-200 ℃, so that the residual of small molecules is extremely low, and the viscosity exposure is hardly increased;
(2) In the application, the peroxide is added into the internal mixer in batches, so that the impact on the modified plastic is less.
(3) In the application, the peroxide is added for 3 times, and the weight ratio of the peroxide to the peroxide is 1 (4-6): (1-5), especially 1:5:3, wherein the influence of the organosilicon master batch on the bending strength of the modified plastic is low;
(4) When banburying for 15-30min is adopted in the application, extruding and granulating are carried out, and the obtained organosilicon master batch is placed for half a year under the high temperature condition without precipitation or sticky problems;
(5) The banburying time is 15-30min, and the problem of unstable granulating particle size and notch problem of the section of the organosilicon master batch, which are possibly caused by the influence of heat under the action of strong extrusion pressure of the polymer due to the organosilicon raw rubber with the weight average molecular weight of 1200000-2000000, are solved by combining the granulating temperature of 160-250 ℃, especially the granulating temperature of 200 ℃.
(6) In the application, each operation step is combined with specific organosilicon raw rubber and polypropylene in the application, so that the fluidity of the obtained organosilicon master batch in the modified polypropylene processing process is increased, and the addition amount of a dispersing agent and a lubricant in the modified plastic processing is effectively reduced.
(7) The organosilicon master batch obtained by the preparation method is not sticky, and the internal mixer grafting reaction process is adopted, so that the master batch has lower small molecule residue and low VOC; the method ensures that the master batch is better and more uniformly dispersed in the modified plastic system, and has smaller influence on the impact performance of the modified plastic.
Detailed Description
The present invention is illustrated by the following specific embodiments, but is not limited to the specific examples given below.
Examples
Example 1
The preparation method of the organic silicon master batch comprises the following steps:
3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane, organosilicon raw rubber with the weight ratio of 1:0.7 and RANPELEN J-560M are added into an internal mixer, internal mixing is carried out for 30min at 120 ℃, wherein 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane is added into the internal mixer for 3 times according to the weight ratio of 1:4:1, the adding interval time is the same, and the mixture is extruded at 160 ℃ for granulation after the internal mixing is finished.
The weight ratio of 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane to the organosilicon raw rubber is 0.1:60.
The silicone rubber contains 0.03-0.05mol% vinyl and has a weight average molecular weight of 1250000-1500000.
Example 2
The preparation method of the organic silicon master batch comprises the following steps:
3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane, organosilicon raw rubber with the weight ratio of 1:2.3 and RANPELEN J-560M are added into an internal mixer, internal mixing is carried out for 15min at 200 ℃, wherein 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane is added into the internal mixer for 3 times according to the weight ratio of 1:6:5, the adding interval time is the same, and the mixture is extruded at 250 ℃ for granulation after the internal mixing is finished.
The weight ratio of 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane to silicone gum is 0.6:60.
The silicone rubber contains 0.03-0.05mol% vinyl and has a weight average molecular weight of 1250000-1500000.
Example 3
The preparation method of the organic silicon master batch comprises the following steps:
adding 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane, organosilicon raw rubber with the weight ratio of 1:1.6 and RANPELEN J-560M into an internal mixer, carrying out internal mixing at 160 ℃ for 20min, wherein 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane is added into the internal mixer for 3 times according to the weight ratio of 1:5:3, the adding interval time is the same, and granulating after the internal mixing is finished at 200 ℃.
The weight ratio of 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane to the organosilicon raw rubber is 0.3:60.
The silicone rubber contains 0.03-0.05mol% vinyl and has a weight average molecular weight of 1250000-1500000.
Example 4
A preparation method of an organosilicon masterbatch is the same as in example 3, except that 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane is added into an internal mixer at one time.
Example 5
The preparation method of the organic silicon master batch comprises the following steps:
adding 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane, organosilicon raw rubber with the weight ratio of 3.5:1.6 and RANPELEN J-560M into an internal mixer, carrying out internal mixing at 160 ℃ for 10min, wherein 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane is added into the internal mixer for 3 times according to the weight ratio of 1:5:3, the adding interval time is the same, and granulating after the internal mixing is finished at 300 ℃.
The weight ratio of 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane to the organosilicon raw rubber is 0.3:60.
The silicone raw rubber was the same as in example 3.
Performance evaluation
2wt% of the silicone master batch obtained in example 3 was added to the modified plastic, respectively, and the test results are shown in Table 1, respectively.
TABLE 1
Wherein, the test conditions and the processing conditions of the products without the organic silicon master batch and with the organic silicon master batch in the table 1 are kept consistent.
Stability: the silicone master batches of 1-5 were placed in an environment of 60 ℃ for half a year, and observed for tackiness, and the test results are shown in table 2.
TABLE 2
Claims (3)
1. The preparation method of the non-precipitation and non-sticky organic silicon master batch is characterized by comprising the following steps of: adding a polymerization reactant and peroxide of the organosilicon master batch into an internal mixer, banburying at 160 ℃, and then extruding and granulating, wherein the peroxide is added into the internal mixer for 3 times;
the polymerization reactants of the organosilicon master batch comprise organosilicon raw rubber with a weight average molecular weight of 1250000-1500000 and polyolefin; the weight ratio of the organosilicon raw rubber to the polyolefin is 1: (0.7-2.3); the organosilicon raw rubber contains vinyl, and the vinyl content is 0.01-0.21mol%; the polyolefin is random copolymer polypropylene;
the peroxide is 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxynonane;
the weight ratio of the peroxide to the organosilicon raw rubber is (0.1-0.6): 60;
the weight ratio of the peroxide to the internal mixer for 3 times is 1 (4-6): (1-5);
the banburying time is 15-30min;
the granulating temperature is 160-250 ℃.
2. The method for producing a non-bleeding, non-sticky silicone masterbatch according to claim 1, characterized in that the granulating temperature is 200 ℃.
3. Use of the non-precipitated, non-tacky silicone master batch prepared by the method for preparing a non-tacky silicone master batch according to any one of claims 1-2 in modified plastics.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102382362A (en) * | 2010-08-30 | 2012-03-21 | 比亚迪股份有限公司 | Scratch resistant material composition as well as scratch resistant material and preparation method thereof |
| CN106147027A (en) * | 2016-07-20 | 2016-11-23 | 上海玉城高分子材料股份有限公司 | A kind of anti-precipitation scratch-resistant polypropylene agglomerate and preparation method thereof |
| CN109503954A (en) * | 2018-10-25 | 2019-03-22 | 武汉金发科技有限公司 | A kind of PP composite material and its preparation method and application |
| CN110358301A (en) * | 2019-07-25 | 2019-10-22 | 成都硅宝科技股份有限公司 | A kind of lasting scratch-resistant organosilicon master batch and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106103577B (en) * | 2014-03-04 | 2020-03-27 | 美国陶氏有机硅公司 | Thermoplastic polymer masterbatch |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102382362A (en) * | 2010-08-30 | 2012-03-21 | 比亚迪股份有限公司 | Scratch resistant material composition as well as scratch resistant material and preparation method thereof |
| CN106147027A (en) * | 2016-07-20 | 2016-11-23 | 上海玉城高分子材料股份有限公司 | A kind of anti-precipitation scratch-resistant polypropylene agglomerate and preparation method thereof |
| CN109503954A (en) * | 2018-10-25 | 2019-03-22 | 武汉金发科技有限公司 | A kind of PP composite material and its preparation method and application |
| CN110358301A (en) * | 2019-07-25 | 2019-10-22 | 成都硅宝科技股份有限公司 | A kind of lasting scratch-resistant organosilicon master batch and preparation method thereof |
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Address after: 201500 1st floor, building 2, 16387 Puwei Road, Shanyang Town, Jinshan District, Shanghai Patentee after: Shanghai Handian New Materials Co.,Ltd. Country or region after: China Address before: 201500 1st floor, building 2, 16387 Puwei Road, Shanyang Town, Jinshan District, Shanghai Patentee before: SHANGHAI HANDIAN TECHNOLOGY Co.,Ltd. Country or region before: China |