CN115558116A - Preparation method and application of non-precipitation and non-stickiness organic silicon master batch - Google Patents
Preparation method and application of non-precipitation and non-stickiness organic silicon master batch Download PDFInfo
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- CN115558116A CN115558116A CN202111559605.0A CN202111559605A CN115558116A CN 115558116 A CN115558116 A CN 115558116A CN 202111559605 A CN202111559605 A CN 202111559605A CN 115558116 A CN115558116 A CN 115558116A
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- master batch
- silicone
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- organic silicon
- internal mixer
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- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 48
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 27
- 239000010703 silicon Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000001556 precipitation Methods 0.000 title description 5
- 150000002978 peroxides Chemical class 0.000 claims abstract description 17
- 239000004033 plastic Substances 0.000 claims abstract description 16
- 229920003023 plastic Polymers 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- 230000001376 precipitating effect Effects 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 6
- 239000000376 reactant Substances 0.000 claims abstract description 6
- 229920001296 polysiloxane Polymers 0.000 claims description 33
- 229920001971 elastomer Polymers 0.000 claims description 15
- 238000005469 granulation Methods 0.000 claims description 9
- 230000003179 granulation Effects 0.000 claims description 9
- 229920000098 polyolefin Polymers 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 2
- 230000000740 bleeding effect Effects 0.000 claims 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000004743 Polypropylene Substances 0.000 description 11
- -1 polypropylene Polymers 0.000 description 10
- 229920001155 polypropylene Polymers 0.000 description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000012545 processing Methods 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
- 239000000314 lubricant Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect 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
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002954 polymerization reaction product Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 150000003384 small molecules Chemical group 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- 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-precipitating and non-sticky organic silicon master batch, and the preparation method of the non-precipitating and non-sticky organic silicon master batch comprises the following steps: and banburying the polymerization reactant of the organic silicon 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 master batch has lower micromolecule residue and low VOC by adopting an internal mixer grafting reaction process; the method ensures that the master batch is better and more uniformly dispersed in a modified plastic system and has less influence on the impact property of the modified plastic.
Description
Technical Field
The invention relates to the technical field of C08K9/06, and particularly relates to a preparation method and application of a non-precipitation and non-stickiness organic silicon master batch.
Background
The scratch resistance of the traditional organosilicon master batch still needs to be improved, and meanwhile, other series of problems exist, for example, chinese patent CN 106243483B synthesizes the scratch resistance agent, the toughening agent, the talcum powder, the lubricant, the light stabilizer, the antioxidant and the polypropylene into a polypropylene material, and the VOC content is reduced to a certain extent by using the supercritical fluid in the preparation process, but the impact performance of the polypropylene material is greatly influenced by the addition of the scratch resistance agent, and the application of the scratch resistance agent is limited to a certain extent. CN 106147027A obtained a polypropylene master batch by using polypropylene, polysiloxane, long-chain alkyl silicone oil and antioxidant, and this master batch had a problem of developing stickiness after a long time.
Disclosure of Invention
In view of the problems in the prior art, the first aspect of the present invention provides a preparation method of a non-precipitating and non-sticky silicone masterbatch, comprising: and banburying the polymerization reactant of the organic silicon 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 an applicant finds in experiments that when the weight average molecular weight of the raw organosilicon rubber is 1200000-2000000 in the application, the viscosity phenomenon of the obtained organosilicon master batch needs to be reduced when a normal-temperature banburying process is adopted, and unexpectedly finds that when the banburying temperature is 120-200 ℃, the viscosity phenomenon of the obtained organosilicon master batch is obviously reduced, and viscosity exposure is not increased.
In one embodiment, the polymerization reaction product of the silicone masterbatch comprises silicone crude rubber with weight-average molecular weight of 1200000-2000000 and polyolefin.
Preferably, the silicone green rubber contains vinyl groups.
Preferably, the vinyl content is from 0.01 to 0.21mol%, more preferably from 0.03 to 0.05mol%.
The silicone raw rubber in the present application can be obtained by a person skilled in the art according to conventional preparation methods.
Preferably, the weight ratio of the silicone green gum to the polyolefin is 1: (0.5-2.5), preferably 1: (0.7-2.3), more preferably 1.
Preferably, the weight ratio of the peroxide to the silicone crude rubber is (0.01-0.6): 60, preferably 0.3.
In one embodiment, the method for preparing the silicone masterbatch comprises: adding the polymerization reactant of the organic silicon master batch and peroxide into an internal mixer, carrying out internal mixing at 120-200 ℃, and then carrying out extrusion granulation, wherein the peroxide is added into the internal mixer for n times, and n is more than or equal to 2.
The applicant processes plastics by adopting conventional organic silicon master batches on the market, finds that the impact performance of the modified plastics is greatly influenced, and unexpectedly finds that the impact performance of the modified plastics is greatly influenced by adding peroxide into an internal mixer in batches, the obtained organic silicon master batches hardly have influence on the impact performance of the modified plastics, and unexpectedly finds that the impact performance is greatly influenced by adding organic silicon raw rubber or polyolefin into the internal mixer in batches.
Preferably, the peroxide is added to the internal mixer in 3 portions.
Preferably, the weight ratio of the peroxide to the internal mixer after 3 times of adding is 1 (4-6): (1-5), more preferably 1.
The peroxide is added to the mixer at the same intervals in this application.
In one embodiment, the banburying is carried out for 15 to 30min, preferably 20min.
In one embodiment, the granulation temperature is 160 to 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 Letian of Korea.
The invention also provides application of the preparation method of the organic silicon master batch without precipitation and stickiness 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 a banburying grafting process, and banburying is carried out at a high temperature of 120-200 ℃, grafting reaction is completed in the banburying process, small molecule residues are extremely low, and viscous exposure is hardly increased;
(2) In the application, the mode of adding peroxide into the internal mixer in batches is adopted, so that the impact on the modified plastic is less.
(3) In the application, peroxide is added for 3 times, and the weight ratio of sequentially adding peroxide is 1 (4-6): (1-5), in particular 1;
(4) When the application adopts banburying for 15-30min, and then extrusion granulation is carried out, the obtained organic silicon master batch has no problems of precipitation and stickiness after being placed under the high temperature condition for half a year;
(5) The banburying time is 15-30min in the application, and the problem of unstable granulation particle size and the problem of gaps of the section of the organic silicon master batch, which are possibly caused by the influence of heat of polymers under the action of strong extrusion pressure due to the organic silicon raw rubber with the weight-average molecular weight of 1200000-2000000, are solved by combining the granulation temperature of 160-250 ℃, particularly the granulation temperature of 200 ℃.
(6) According to the application, the specific organic silicon crude rubber and the specific polypropylene in the application are combined in each operation step, so that the fluidity of the obtained organic silicon master batch in the processing process of the modified polypropylene is increased, and the addition amounts of the dispersing agent and the lubricating agent in the processing of the modified plastic are effectively reduced.
(7) The organosilicon master batch obtained by the preparation method is not sticky, and the master batch has lower micromolecule residue and low VOC by adopting an internal mixer grafting reaction process; the method ensures that the master batch is better and more uniformly dispersed in a modified plastic system and has less influence on the impact property 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
A preparation method of an organic silicon master batch comprises the following specific steps:
3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane, together with silicone gum and RANPELEN J-560M in a weight ratio of 1.
The weight ratio of 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane to silicone crude gum was 0.1.
The silicone crude rubber contains 0.03-0.05mol% of vinyl and has the weight-average molecular weight of 1250000-1500000.
Example 2
A preparation method of an organic silicon master batch comprises the following specific steps:
3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane and 2.3 parts by weight of organosilicon crude rubber and RANPELEN J-560M are added into an internal mixer and internally mixed for 15min at 200 ℃, wherein the 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.
The weight ratio of 3,6,9-triethyl-3,6,9-trimethyl-1, 4, 7-triperoxonane to silicone gum was 0.6.
The silicone crude rubber contains 0.03-0.05mol% of vinyl and has the weight-average molecular weight of 1250000-1500000.
Example 3
A preparation method of an organic silicon master batch comprises the following specific steps:
3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane and 1.6 by weight of silicone crude rubber and RANPELEN J-560M are added into an internal mixer and internally mixed for 20min at 160 ℃, wherein the 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane is added into the internal mixer in 3 times according to the weight ratio of 1.
The weight ratio of 3,6,9-triethyl-3,6,9-trimethyl-1, 4, 7-triperoxonane to silicone gum was 0.3.
The silicone crude rubber contains 0.03-0.05mol% of vinyl and has a weight-average molecular weight of 1250000-1500000.
Example 4
A process for preparing an organosilicon masterbatch, similar to example 3, except that 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane was added to the internal mixer at once.
Example 5
A preparation method of an organic silicon master batch comprises the following specific steps:
3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane and 3.5 weight ratio of organosilicon crude rubber and RANPELEN J-560M are added into an internal mixer and internally mixed for 10min at 160 ℃, wherein the 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane is added into the internal mixer according to the weight ratio of 1.
The weight ratio of 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane to silicone crude gum was 0.3.
The silicone green was the same as in example 3.
Performance evaluation
2wt% of the organosilicon master batch obtained in example 3 was added to the modified plastic, and the test results are shown in Table 1.
TABLE 1
In table 1, the test conditions and processing conditions of the products without adding the silicone master batch and with adding the silicone master batch are consistent.
Stability: respectively placing 1-5 organic silicon master batches in an environment of 60 ℃ for half a year, observing whether the organic silicon master batches are sticky or not, and the test results are shown in table 2.
TABLE 2
Claims (10)
1. A preparation method of a non-precipitating and non-sticky organic silicon master batch is characterized by comprising the following steps: and banburying the polymerization reactant of the organic silicon master batch and peroxide in an internal mixer at 120-200 ℃, and then extruding and granulating.
2. The preparation method of the non-precipitating and non-sticky silicone master batch according to claim 1, wherein the preparation method of the silicone master batch comprises the following steps: adding the polymerization reactant of the organic silicon master batch and peroxide into an internal mixer, carrying out internal mixing at 120-200 ℃, and then carrying out extrusion granulation, wherein the peroxide is added into the internal mixer for n times, and n is more than or equal to 2.
3. The method for preparing the non-bleeding, non-tacky silicone masterbatch according to claim 2, wherein n is 3.
4. The preparation method of the non-precipitating and non-sticky organic silicon master batch according to claim 3, wherein the weight ratio of the peroxide added into the internal mixer for 3 times is 1 (4-6): (1-5).
5. The method for preparing the non-bleeding, non-tacky silicone masterbatch according to any one of claims 1 to 4, wherein the polymerization reactants of the silicone masterbatch comprise silicone raw gum having a weight average molecular weight of 1200000 to 2000000 and polyolefin.
6. The method for preparing the non-precipitating and non-sticky silicone master batch according to claim 5, wherein the weight ratio of the silicone raw rubber to the polyolefin is 1: (0.5-2.5).
7. The preparation method of the non-precipitating and non-sticky silicone master batch according to claim 6, wherein the banburying time is 15-30min.
8. The method for preparing the non-bleeding, non-tacky silicone masterbatch according to claim 7, wherein the temperature of the granulation is 160-250 ℃.
9. The method of preparing the non-bleeding, non-tacky silicone masterbatch according to claim 8, wherein the temperature of the granulation is 200 ℃.
10. Use of the no-bleed, no-tack silicone masterbatch of any one of claims 1-9 in a modified plastic.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111559605.0A CN115558116B (en) | 2021-12-20 | 2021-12-20 | Preparation method and application of non-precipitation non-sticky organic silicon master batch |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111559605.0A CN115558116B (en) | 2021-12-20 | 2021-12-20 | Preparation method and application of non-precipitation non-sticky organic silicon master batch |
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| CN115558116A true CN115558116A (en) | 2023-01-03 |
| CN115558116B CN115558116B (en) | 2024-03-12 |
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Citations (5)
| 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 |
| US20170058114A1 (en) * | 2014-03-04 | 2017-03-02 | Dow Corning Corporation | Thermoplastic polymer masterbatch |
| 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 |
-
2021
- 2021-12-20 CN CN202111559605.0A patent/CN115558116B/en active Active
Patent Citations (5)
| 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 |
| US20170058114A1 (en) * | 2014-03-04 | 2017-03-02 | Dow Corning Corporation | Thermoplastic polymer masterbatch |
| 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 |