CN115572482B - High scratch-resistant organosilicon additive and application thereof - Google Patents
High scratch-resistant organosilicon additive and application thereof Download PDFInfo
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- CN115572482B CN115572482B CN202111571715.9A CN202111571715A CN115572482B CN 115572482 B CN115572482 B CN 115572482B CN 202111571715 A CN202111571715 A CN 202111571715A CN 115572482 B CN115572482 B CN 115572482B
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- organosilicon
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- polypropylene
- peroxide
- additive
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- 239000000654 additive Substances 0.000 title claims abstract description 31
- 230000000996 additive effect Effects 0.000 title claims abstract description 30
- 230000003678 scratch resistant effect Effects 0.000 title claims abstract description 22
- -1 polypropylene Polymers 0.000 claims abstract description 52
- 239000004743 Polypropylene Substances 0.000 claims abstract description 48
- 229920001155 polypropylene Polymers 0.000 claims abstract description 45
- 229920001971 elastomer Polymers 0.000 claims abstract description 33
- 150000002978 peroxides Chemical class 0.000 claims abstract description 17
- 229920006163 vinyl copolymer Polymers 0.000 claims abstract description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 239000010703 silicon Substances 0.000 claims abstract description 5
- 239000000155 melt Substances 0.000 claims description 16
- 229920001296 polysiloxane Polymers 0.000 claims description 14
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 9
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 23
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 229920002379 silicone rubber Polymers 0.000 description 10
- 239000004945 silicone rubber Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000005452 bending Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 229920005680 ethylene-methyl methacrylate copolymer Polymers 0.000 description 1
- DIRFUJHNVNOBMY-UHFFFAOYSA-N fenobucarb Chemical compound CCC(C)C1=CC=CC=C1OC(=O)NC DIRFUJHNVNOBMY-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
Abstract
The invention relates to a high scratch-resistant organosilicon additive (IPC class number: C08G 18/80), in particular to a high scratch-resistant organosilicon additive and application thereof. The raw materials at least comprise the following components in parts by weight: 30-60 parts of organosilicon raw rubber, 40-70 parts of polypropylene, 0.01-0.3 part of peroxide and 10-20 parts of vinyl copolymer. The invention prepares the high scratch-resistant organosilicon additive, and the prepared organosilicon additive has good scratch resistance and mechanical property through the synergistic effect of DBPMH, cPP and organosilicon raw rubber. Meanwhile, the prepared organic silicon additive has low odor, and is added into the polypropylene material, and when the addition amount is 1-2wt%, the polypropylene material also has good scratch resistance and excellent mechanical property.
Description
Technical Field
The invention relates to a high scratch-resistant organosilicon additive (IPC class number: C08G 18/80), in particular to a high scratch-resistant organosilicon additive and application thereof.
Background
The polypropylene material has good mechanical property and processability, has the advantages of recoverability, light weight, low cost and the like, and is applied to more fields, however, the high scratch resistance of the polypropylene material is poor, the poor scratch resistance becomes the most important factor influencing the appearance and service life of the polypropylene material, so that the application of the polypropylene material is greatly limited, the polypropylene material which is improved for the problems is currently available on the market, but the high scratch resistance of the material is mostly increased by adding various powder fillers into the polypropylene matrix resin, so that the high scratch resistance of the material is effectively improved, but the density of the material is greatly increased by adding the powder, so that the weight of the polypropylene material is greatly improved, and the polypropylene material is difficult to be applied to the field with the light weight requirement. Patent application cn201811210672.X discloses a scratch-resistant polypropylene composite material, wherein a large amount of toughening material is added into the composite material, so that the polypropylene material has good scratch resistance, but the addition of spherical silicon powder greatly increases the weight of the polypropylene material, and the use of polypropylene is limited. Therefore, development of an additive with high scratch resistance is urgently needed at present, and the additive is applied to polypropylene filler, so that the polypropylene material has good high scratch resistance.
The invention prepares the high scratch-resistant organosilicon additive, and the prepared organosilicon additive has good scratch resistance and mechanical property through the synergistic effect of DBPMH, cPP and organosilicon raw rubber. Meanwhile, the prepared organic silicon additive has small smell, and is added into the polypropylene material, and when the addition amount is 1-2wt%, the polypropylene material also has good scratch resistance and excellent mechanical property.
Disclosure of Invention
In order to solve the above problems, a first aspect of the present invention provides a high scratch resistant silicone additive, comprising, in parts by weight: 30-60 parts of organosilicon raw rubber, 40-70 parts of polypropylene, 0.01-0.3 part of peroxide and 10-20 parts of vinyl copolymer.
As a preferred scheme, the high scratch-resistant organosilicon additive comprises the following raw materials in parts by weight: 40 to 50 parts of organosilicon raw rubber, 50 to 60 parts of polypropylene, 0.15 to 0.2 part of peroxide and 12 to 17 parts of vinyl copolymer
As a preferred embodiment, the silicone rubber is a block, granule or powder rubber which is in an uncrosslinked state and has fluidity.
As a preferable scheme, the vinyl content of the organosilicon raw rubber accounts for 0.01-0.1% of the mole fraction of the organosilicon raw rubber.
As a preferable scheme, the vinyl content of the organosilicon raw rubber accounts for 0.03-0.05% of the mole fraction of the organosilicon raw rubber.
As a preferable scheme, the weight average relative molecular weight of the organosilicon raw rubber is 120 ten thousand to 200 ten thousand.
As a preferred embodiment, the silicone rubber is one or more of methyl vinyl silicone rubber and methyl phenyl vinyl rubber.
As a preferred embodiment, the silicone rubber is methyl vinyl silicone rubber.
As a preferred embodiment, the silicone gum is commercially available from Shanghai culvert science and technology Inc.
As a preferred embodiment, the polypropylene is a copolypropylene (cPP).
As a preferred embodiment, the cPP is a mixture of cPP having a melt flow rate of 5 to 8g/10min and cPP having a melt flow rate of 30 to 35g/10 min.
As a preferred embodiment, the ratio by weight of cPP having a melt flow rate of 5 to 8g/10min to cPP having a melt flow rate of 30 to 35g/10min is (0.7 to 0.9): 1.
as a preferred embodiment, the cPP with a melt flow rate of 5-8 g/10min is K8025, purchased from Taiwan.
As a preferred embodiment, the cPP having a melt flow rate of 30 to 35g/10min is K3029, purchased from Taiwan.
As a preferred embodiment, the peroxide is an alkyl peroxide.
As a preferred embodiment, the alkyl peroxide is one or more of 1, 1-di-t-butylperoxy-3, 3-trimethylcyclohexane (BPMC), 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane (DBPMH), and di-t-butyl peroxide (DTBP).
As a preferred embodiment, the alkyl peroxide is DBPMH.
As a preferable scheme, the weight ratio of the polypropylene to the peroxide is (320-330): 1.
as a preferable scheme, the weight ratio of the polypropylene to the peroxide is (325-327): 1.
as a preferred embodiment, the vinyl copolymer is one or more of ethylene-octene copolymer (POE), ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-propylene-butadiene terpolymer, ethylene-n-butyl acrylate-carbonyl terpolymer.
As a preferred embodiment, the ethylene copolymer is an ethylene-methyl acrylate copolymer (POE).
As a preferred embodiment, the POE has a hardness of 65 to 75shore a; the melt index of POE is 0.5-1.3 g/10min (190 ℃/2.16 kg).
As a preferred embodiment, the POE is one or more of DF810, DF710, engage 8150.
As a preferred embodiment, the POE is Engage 8150, available from Dow in the United states.
As a preferred scheme, the weight ratio of the vinyl copolymer to the polypropylene is 1: (3.5-4).
As a preferred scheme, the weight ratio of the vinyl copolymer to the polypropylene is 1:3.7.
as a preferred embodiment, the weight ratio of the peroxide to the vinyl copolymer is 1: (85-90).
The second aspect of the present invention provides a method for preparing a high scratch resistant silicone additive, comprising the steps of:
the organosilicon raw rubber, polypropylene, peroxide and vinyl copolymer are proportionally put into an internal mixer to be subjected to internal mixing reaction for 15-30 min at 25 ℃, and then are granulated at 160-250 ℃ to obtain the high scratch-resistant organosilicon additive.
According to the invention, the vinyl content, the molecular weight and the weight ratio of cPP and DBPMH of the organosilicon raw rubber are limited, so that the crosslinking reaction of the organosilicon rubber and the cPP is improved, the bending strength of the product is improved, the dispersion degree of the product in the polypropylene material is improved, namely, the addition amount is 1-2%, and the high scratch resistance of the polypropylene material can be realized. The applicant speculates that DBPMH in the present invention may promote cPP degradation, and the random structure of cPP facilitates migration of silicone to its surface, and that the degraded cPP reacts with the vinyl groups of the silicone gum to form a cPP-silicone gum copolymer. Further, the applicant found through a large number of experiments that when the vinyl content of the silicone rubber was too large, crosslinking was likely to occur, which was unfavorable for dispersion and migration to the surface, but when the vinyl content of the silicone rubber was too small, grafting of cPP was unfavorable, and tackiness was likely to be precipitated. Meanwhile, the application has unexpectedly found in experiments that when the weight average relative molecular weight of the organosilicon raw rubber is 120-200 ten thousand, the scratch resistance of polypropylene is optimal.
The beneficial effects are that:
1. the weight ratio of DBPMH to POE is defined as 1: (85-90), the impact strength of the product is improved, meanwhile, the crystallization of POE can be inhibited, and the interface performance of the organosilicon raw rubber and the polypropylene is effectively improved.
2. The application defines the weight ratio of cPP to DBPMH as (300-310): 1, the crosslinking reaction of the organic silicon rubber and the cPP is improved, so that the bending strength of the product is improved, the dispersion degree of the product in the polypropylene material is also improved, namely, the addition amount is 1-2%, and the high scratch resistance of the polypropylene material can be realized.
3. The vinyl content of the organosilicon raw rubber is limited to be 0.01-0.1% and when the weight-average molecular weight is 120-200 ten thousand, the dispersion and the compatibility of the organosilicon raw rubber with the cPP are improved, and meanwhile, the crosslinking of the cPP and the organosilicon raw rubber is facilitated to form a stable cPP-organosilicon copolymer, and the tensile strength and scratch resistance of the product are improved.
4. The invention effectively improves the processing performance of the mixed system and simultaneously improves the compatibility between polypropylene and organosilicon crude rubber through the synergistic effect of the cPP with the melt flow rate of 5-8 g/10min and the cPP with the melt flow rate of 30-35 g/10 min.
5. According to the invention, through the synergistic effect of Engage 8150 and cPP, the compatibility of a blending system is effectively improved, the dispersion of polypropylene is facilitated, and the notch impact strength of the product is improved.
Detailed Description
Examples
Example 1
The embodiment 1 of the invention provides a high scratch-resistant organic silicon additive, which comprises the following raw materials in parts by weight: 45 parts of organosilicon raw rubber, 55.5 parts of polypropylene, 0.17 part of peroxide and 15 parts of vinyl copolymer
The vinyl content of the silicone raw rubber in this example was 0.04% by mole of the silicone raw rubber.
The weight average relative molecular weight of the silicone raw rubber monomer in this example was 150 ten thousand.
The silicone rubber in this example was methyl vinyl silicone rubber purchased from Shanghai culvert technologies.
The polypropylene in this embodiment is cPP.
The weight ratio of cPP having a melt flow rate of 6.5g/10min to cPP having a melt flow rate of 32g/10min in this example was 0.15:1.
the cPP with a melt flow rate of 6.5g/10min in this example was K8025, purchased from Taiwan.
The cPP with a melt flow rate of 32g/10min in this example was K3029, purchased from Taiwan.
The peroxide in this example was DBPMH, purchased from Hubei Xin bonus chemical Co.
The ethylene copolymer in this example is POE.
POE in this example is Engage 8150, purchased from Dow in the United states.
The preparation method of the high scratch-resistant organic silicon additive in the embodiment mainly comprises the following steps: the organosilicon raw rubber, polypropylene, peroxide and vinyl copolymer are proportionally put into an internal mixer to carry out internal mixing reaction for 20min at 25 ℃, and then pelleting is carried out at 200 ℃ to obtain the organosilicon additive with high scratch resistance.
And melting and granulating the prepared high scratch-resistant organosilicon additive PP+T20.
The amount of the high scratch resistant silicone additive added in this example was 0.26% by mass of pp+t20.
PP+T20 in this example is a modified polypropylene plastic product purchased from Shanghai culvert science and technology Co.
Comparative example 1
And melting and granulating the outsourced organosilicon additive PP+T20.
The addition amount of the silicone additive in this comparative example was 0.26% by mass of pp+t20.
The silicone additives described in this comparative example were purchased from FSX801 of shanghai strontium Ming rubber and plastic technologies limited.
In this comparative example, the pp+t20 was purchased from Shanghai culvert technologies limited.
Performance test:
(1) Scratch resistance grade Δl: according to PV-3952.
(2) Smell: according to PV-3900.
(3) Viscosity: according to PV-1306.
(4) Tensile strength: according to ISO-527.
(5) Flexural strength: according to ISO-178.
(6) Cantilever beam notch impact: according to ISO-180.
Performance test results:
table 1 shows the results of the performance tests of example 1 and comparative example 1.
TABLE 1
| Project | Example 1 | Comparative example 1 |
| ΔL | 0.68 | 2.31 |
| Smell of materials | 3.5 | 4 |
| Viscous exposure | 1 | 1 |
| Tensile Strength/MPa | 36.1 | 35.9 |
| Flexural Strength/MPa | 38.5 | 38.9 |
| Izod notched impact KJ/m 2 | 5.2 | 4.7 |
In this embodiment, pp+t20 is the same batch.
Claims (3)
1. The high scratch-resistant organosilicon additive is characterized by comprising the following raw materials in parts by weight: 30-60 parts of organosilicon raw rubber, 40-70 parts of polypropylene, 0.01-0.3 part of peroxide and 10-20 parts of vinyl copolymer;
the vinyl content of the organosilicon raw rubber accounts for 0.03-0.05% of the mole fraction of the organosilicon raw rubber; the weight average relative molecular weight of the organosilicon raw rubber is 120-200 ten thousand;
the vinyl copolymer is POE, and the hardness of the POE is 65-75 Shore A; the melt index of POE is 0.5-1.3 g/10min;
the polypropylene is cPP; the cPP is a mixture of cPP with a melt flow rate of 5-8 g/10min and cPP with a melt flow rate of 30-35 g/10min;
the peroxide is alkyl peroxide; the alkyl peroxide is DBPMH;
the weight ratio of the polypropylene to the peroxide is (320-330): 1, a step of;
the weight ratio of the peroxide to the vinyl copolymer is 1: (85-90);
the preparation method of the high scratch-resistant organic silicon additive mainly comprises the following steps: the organosilicon raw rubber, polypropylene, peroxide and vinyl copolymer are proportionally put into an internal mixer to be subjected to internal mixing reaction for 15-30 min at 25 ℃, and then are granulated at 160-250 ℃ to obtain the high scratch-resistant organosilicon additive.
2. The high scratch resistant silicone additive of claim 1, wherein the raw materials comprise, in parts by weight: 40-50 parts of organosilicon raw rubber, 50-60 parts of polypropylene, 0.15-0.2 part of peroxide and 12-17 parts of vinyl copolymer.
3. Use of a high scratch resistant silicone additive according to any of claims 1-2 in polypropylene filler systems.
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| CN202111571715.9A CN115572482B (en) | 2021-12-21 | 2021-12-21 | High scratch-resistant organosilicon additive and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111571715.9A CN115572482B (en) | 2021-12-21 | 2021-12-21 | High scratch-resistant organosilicon additive and application thereof |
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| CN115572482B true CN115572482B (en) | 2024-01-26 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN111363366A (en) * | 2020-03-26 | 2020-07-03 | 成都硅宝科技股份有限公司 | Crosslinkable durable scratch-resistant organic silicon master batch and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100475946B1 (en) * | 2002-06-05 | 2005-03-10 | 한일이화주식회사 | Polypropylene resin composition for a automobile door trim having superior impact resistance and scratch resistance properties |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN111363366A (en) * | 2020-03-26 | 2020-07-03 | 成都硅宝科技股份有限公司 | Crosslinkable durable scratch-resistant organic silicon master batch and preparation method thereof |
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