CN112029296B - Organic carrier-free polysiloxane particles and preparation method thereof - Google Patents
Organic carrier-free polysiloxane particles and preparation method thereof Download PDFInfo
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- CN112029296B CN112029296B CN202010983409.5A CN202010983409A CN112029296B CN 112029296 B CN112029296 B CN 112029296B CN 202010983409 A CN202010983409 A CN 202010983409A CN 112029296 B CN112029296 B CN 112029296B
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- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 179
- -1 polysiloxane Polymers 0.000 title claims abstract description 140
- 239000002245 particle Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000006229 carbon black Substances 0.000 claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 51
- 239000000945 filler Substances 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 24
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 238000004898 kneading Methods 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- 239000000969 carrier Substances 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 239000007822 coupling agent Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 241000227425 Pieris rapae crucivora Species 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 150000004645 aluminates Chemical class 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229920002545 silicone oil Polymers 0.000 claims description 3
- 238000012545 processing Methods 0.000 abstract description 12
- 229920005992 thermoplastic resin Polymers 0.000 abstract description 6
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 38
- 230000000052 comparative effect Effects 0.000 description 17
- 238000005469 granulation Methods 0.000 description 13
- 230000003179 granulation Effects 0.000 description 13
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000314 lubricant Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- 239000008187 granular material Substances 0.000 description 5
- 238000013508 migration Methods 0.000 description 5
- 230000005012 migration Effects 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229920000092 linear low density polyethylene Polymers 0.000 description 4
- 239000004707 linear low-density polyethylene Substances 0.000 description 4
- 230000001050 lubricating effect Effects 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 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 3
- 230000000694 effects Effects 0.000 description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000000051 modifying effect Effects 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 108010054404 Adenylyl-sulfate kinase Proteins 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 241000872198 Serjania polyphylla Species 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- BQRPSOKLSZSNAR-UHFFFAOYSA-N ethenyl-tris[(2-methylpropan-2-yl)oxy]silane Chemical compound CC(C)(C)O[Si](OC(C)(C)C)(OC(C)(C)C)C=C BQRPSOKLSZSNAR-UHFFFAOYSA-N 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- RJSYPKWVIJGNLO-UHFFFAOYSA-N CCOClOC Chemical compound CCOClOC RJSYPKWVIJGNLO-UHFFFAOYSA-N 0.000 description 1
- 102100039024 Sphingosine kinase 1 Human genes 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000004597 plastic additive Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- 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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
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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)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention belongs to the field of high polymer materials, and provides a preparation method of organic carrier-free polysiloxane particles, which comprises the following steps: s1, polysiloxane, white carbon black, a grafting agent and a catalyst A are reacted and mixed in a kneading machine or an internal mixer to prepare a high-viscosity polysiloxane composition; the polysiloxane contains 0.02 to 0.2 percent of vinyl; s2, mixing the high-viscosity polysiloxane composition prepared in the step S1 and a filler in a kneader or an internal mixer, extruding and granulating to prepare the organic carrier-free polysiloxane particles. The method has the advantages of simple process flow, safe and easily-produced raw materials, excellent product performance and good application and popularization prospects. The invention also provides the organic carrier-free polysiloxane particles prepared by the method, which are applicable to almost all thermoplastic resin processing, can improve the processing flowability of the thermoplastic resin, and can improve the surface smoothness of products, reduce the surface friction coefficient, improve the wear resistance and scratch resistance and the like.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to organic carrier-free polysiloxane particles and a preparation method thereof.
Background
The organosilicon material is a special high molecular material with a semi-organic and semi-inorganic structure and has unique excellent performance. The organic silicon lubricant is a plastic lubricant, comprises silicone master batches and silicone powder, and has wide application in the fields of plastic modification, pipes, films, automotive interiors, wires and cables and the like.
The MB50 lubricant series products, which are first introduced by Dow Corning company in America, are silicone master batches which take ultra-high molecular weight silicone as a lubricating active ingredient and take different resins as carriers, and the dosage of the silicone master batches is generally about 0.2-5% in the plastic processing process. The silicone master batch overcomes the defects that the traditional organic silicon plastic additive and plastic are difficult to be uniformly mixed and migrate to the surface of a product, and is easy to add; however, different silicone masterbatches with different carriers are selected for different material systems, so that the application range of the silicone masterbatches is limited. The silicone powder is used as another silicone lubricant, and has the problems of small addition amount, uneven mixing with granular products and easy uneven product quality. Therefore, the existing silicone master batch containing the organic carrier and the silicone powder both have certain defects.
To solve the above-mentioned disadvantages, silicone particles free of organic carriers are commercially available, which are suitable for the processing of virtually all thermoplastics and are suitable for direct extrusion or injection molding. The modified polypropylene composite material is used in the plastic processing process, so that on one hand, the flowability of polymer resin in a molten state can be improved, the dispersion of fillers is improved, the energy consumption of extrusion injection molding processing is reduced, and the production efficiency is improved; on the other hand, the surface smoothness of the product can be improved, the surface friction coefficient is reduced, the wear resistance and scratch resistance are improved, and the like.
Since silicone particles without organic carrier have excellent properties, the preparation of silicone particles without organic carrier has become one of the hot spots in the development of the prior art, and patent application No. CN200410062075.9 discloses a granular organopolysiloxane material prepared by mixing polysiloxane, silica, and other fillers, additives, etc. through a special granulating device; the preparation method of the organic polysiloxane material particularly points out that boric acid and water are added, otherwise, the polysiloxane cannot be prepared into particles and is easy to adhere to a porous plate and a knife.
However, in 6 months 2010, the european chemical administration (ECHA) lists boric acid as a REACH high concern Substance (SVHC), so that the application of boric acid is further limited, and thus the use and popularization of the method is limited.
Disclosure of Invention
The invention aims to provide a preparation method of polysiloxane particles without organic carriers, which has the advantages of simple process flow, safe and easily produced raw materials, excellent product performance and good application and popularization prospects.
It is another object of the present invention to provide organopolysiloxane particles free of organic carrier, which are suitable for almost all thermoplastic resin processing, can improve the processing flowability of the thermoplastic resin, and can improve the surface smoothness of articles, reduce the surface friction coefficient, and improve the wear and scratch resistance, etc.
The invention is realized by the following technical scheme:
the invention provides a preparation method of polysiloxane particles without organic carriers, which is characterized by comprising the following steps:
s1, reacting and mixing polysiloxane, white carbon black, a grafting agent and a catalyst A in a kneading machine or an internal mixer for 0.5-3 h to prepare a high-viscosity polysiloxane composition; the polysiloxane contains 0.02 to 0.2 percent of vinyl;
s2, mixing the high-viscosity polysiloxane composition prepared in the step S1 and a filler in a kneader or an internal mixer, extruding and granulating to prepare the organic carrier-free polysiloxane particles.
The invention also provides polysiloxane particles without organic carriers, which are prepared by the preparation method.
The invention has the beneficial effects that:
1. according to the invention, the vinyl-containing polysiloxane, the white carbon black, the grafting agent and the catalyst A are melted, mixed and fully reacted, and the white carbon black with a large number of hydrogen bonds on the surface can be subjected to hydrosilylation reaction with the vinyl-containing polysiloxane, so that the white carbon black is grafted on the surface of the polysiloxane, meanwhile, the polysiloxane is subjected to chain extension reaction, under the dual actions of grafting the white carbon black and chain extension, the viscosity of the polysiloxane is increased, and the inorganic white carbon black is uniformly and stably loaded in the polysiloxane, so that the polysiloxane is easier to granulate, and the organic carrier-free polysiloxane particles can be prepared without adding other limited raw materials additionally.
2. The organic carrier-free polysiloxane particles prepared by the preparation method are almost suitable for processing all thermoplastic resins, can improve the processing fluidity of the thermoplastic resins, and can improve the surface smoothness of products, reduce the surface friction coefficient, improve the wear resistance and scratch resistance and the like.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below.
The invention provides a preparation method of polysiloxane particles without organic carriers, which comprises the following steps: s1, reacting and mixing polysiloxane, white carbon black, a grafting agent and a catalyst A in a kneading machine or an internal mixer for 0.5-3 h to prepare a high-viscosity polysiloxane composition; the polysiloxane contains 0.02 to 0.2 percent of vinyl; s2, melting, mixing and extruding the high-viscosity polysiloxane composition prepared in the step S1 and a filler for granulation to prepare the organic carrier-free polysiloxane particles.
According to the invention, the vinyl-containing polysiloxane, the white carbon black, the grafting agent and the catalyst A are subjected to a melt mixing reaction, and the white carbon black with a large number of hydrogen bonds on the surface can be subjected to a hydrosilylation reaction with the vinyl-containing polysiloxane, so that the white carbon black is grafted on the surface of the polysiloxane, and meanwhile, the polysiloxane is subjected to a chain extension reaction, so that the viscosity of the polysiloxane is increased and the inorganic white carbon black is uniformly and stably loaded in the polysiloxane under the dual actions of the grafted white carbon black and the chain extension, so that the polysiloxane is easier to granulate, and the organic carrier-free polysiloxane particles can be prepared without adding other limited raw materials additionally.
In particular, the polysiloxanes of the invention are selected from those having a viscosity of 106～107Linear polysiloxanes of mPaS. With a viscosity of 106～107modifying mPas-containing ultrahigh molecular weight polysiloxane, granulating, and granulatingThe siloxane has ultrahigh viscosity, so that the prepared polysiloxane particles have higher hardness, the better granulation performance of the polysiloxane can be ensured without adding water or an organic carrier, and the organic carrier-free polysiloxane particles can be conveniently and efficiently prepared. Meanwhile, linear polysiloxane is selected, and the prepared polysiloxane particles have better action effect when being applied to the processing process of thermoplastic plastics.
More specifically, the polysiloxanes selected for use in the present invention have a viscosity of 10 at room temperature6～107mPaS, measured by a HAAKE MARS rotational viscometer at 25 ℃ in creep recovery mode at 50Pa at 25 ℃. In addition, the polysiloxane chain segment contains hydroxyl besides vinyl, the weight average molecular weight of the polysiloxane is 50-90 ten thousand, and the penetration degree is 180-400.
The high-viscosity silicone composition obtained after the reaction and mixing in step S1 had a viscosity of 108～109mPa · S. It is thus fully demonstrated that the viscosity of the polysiloxane is greatly increased after step S1 of the present invention.
In step S1 of the present invention, the white carbon black may be selected from common white carbon black or modified white carbon black; preferably, modified white carbon black is selected; specifically, the modified white carbon black is prepared by kneading 100 parts of common white carbon black, 1-10 parts of silane coupling agent containing vinyl and 0.001-0.1 part of catalyst B in a kneading machine at 50-200 ℃; the common white carbon black comprises one or two of silicon dioxide prepared by a gas phase method or a precipitation method; the silane coupling agent containing vinyl is selected from one or more of vinyl trichlorosilane, vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tri-tert-butoxy silane or vinyl triacetoxy silane; the catalyst B is selected from an acid-base catalyst or a heavy metal salt catalyst; wherein the acid-base catalyst can be at least one selected from sulfuric acid, phosphoric acid, hydrochloric acid, acetic acid, sodium hydroxide, potassium hydroxide and organic amine; the heavy metal salt catalyst is at least one selected from Pt, Rh, Sn, Ni, Co and compounds or complexes thereof.
The common white carbon black is modified by the method, and hydroxyl groups on the white carbon black are used for grafting reaction, so that vinyl groups are grafted to the white carbon black, the surface of the common white carbon black is grafted with vinyl groups, and the modified white carbon black containing the vinyl groups and the hydroxyl groups is grafted to the surface of polysiloxane more easily and more stably in the reaction of the step S1, so that the viscosity of the polysiloxane is increased more easily.
In step S1 of the present invention, catalyst a is selected from Pt, Rh, Ni, Co and compounds or complexes thereof; preferably selecting Pt and compounds or complexes thereof, wherein the Pt content is 500-1000 ppm or the standard commonly used in the market; the grafting agent is any one of hydrogen-containing silicone oil containing at least 2 Si-H bonds, and the hydrogen content is 0.01-0.80 wt%.
In order to improve the viscosity of the polysiloxane more, in step S1 of the present invention, the weight ratio of each raw material satisfies: 100 parts of polysiloxane, 4-20 parts of white carbon black, 0.001-0.10 part of grafting agent and 0.01-100 parts of catalyst A. Preferably, in step S1, the weight ratio of each raw material satisfies: 100 parts of polysiloxane, 8-18 parts of white carbon black, 0.005-0.05 part of grafting agent and 0.1-50 parts of catalyst A. More preferably, in step S1, the weight ratio of each raw material satisfies: 100 parts of polysiloxane, 10-15 parts of white carbon black, 0.01-0.05 part of grafting agent and 0.1-5 parts of catalyst A. Within the range of the raw material proportion, the white carbon black can well participate in the reaction, and the surface grafting rate of the polysiloxane can reach the best, so that the hardness of the prepared high-viscosity polysiloxane composition is well improved.
In order to meet better granulation conditions and avoid the situation that the granules are sticky and difficult to granulate, the filler is added in step S2, and in order to ensure the uniform mixing of the filler and polysiloxane, the modified filler is preferably added and is prepared by treating the common filler with a surface treating agent; the surface treating agent is selected from one or more of silane coupling agent, titanate coupling agent or aluminate coupling agent. The surface modification treatment is carried out on the filler through the coupling agent, so that the dispersing capacity of the polysiloxane and the interface bonding force between the polysiloxane and the filler are improved, the filler is added into the polysiloxane and can be uniformly mixed with the polysiloxane, the hardness of the obtained mixture is further increased, and the granulation is facilitated.
The general formula of the silane coupling agent is RSiZ3Wherein R is an organic group such as a vinyl group, an epoxy group, a methacrylate group, a thiol group, or the like; z is an alkoxy group capable of hydrolysis, such as methoxy, ethoxy, chlorine, and the like.
The common filler is selected from one or more of silicon dioxide, light calcium carbonate, heavy calcium carbonate, talcum powder, kaolin, quartz powder, carbon black, clay, diatomite or mica powder; the silicon dioxide comprises gas phase method and precipitation method, the particle size of the common filler is 0.1-100 mu m, and the specific surface area is 50-400 m2/g。
Preferably, the weight ratio of the high viscosity polysiloxane composition and the filler satisfies: 100: 20-80. Specifically, when 100 parts of the high viscosity polysiloxane viscosity composition prepared is selected to have a viscosity of 107～108When the viscosity of the siloxane particles is mPa.S, the filler amount is 50-80 parts, so that the viscosity of the siloxane particles is more than or equal to 10 in the extrusion granulation process10mPa.S, the hardness is more than or equal to 35 HA; or selecting 100 parts of high-viscosity polysiloxane with viscosity of 108～109When the viscosity of the siloxane particles is mPa.S, the inorganic filler is 20-50 parts, so that the viscosity of the siloxane particles is more than or equal to 10 in the extrusion granulation process10mPa.S, the hardness is more than or equal to 35HA, and the sticking phenomenon can not be caused in the granulation process.
In step S2 of the present invention, besides the above filler, an anti-violet antioxidant, a dispersant, a compatibilizer, a silane coupling agent or a titanate coupling agent may be added according to actual requirements.
Specifically, in step S2, the high-viscosity polysiloxane composition and the filler are firstly added into an internal mixer or a kneader and mixed for 0.5 to 6 hours at 50 to 200 ℃; and then feeding the mixed material into a reciprocating single-screw extruder or a double-screw extruder through double cones, and extruding and granulating at 50-200 ℃. The temperature in the mixing stage is preferably 150 ℃, and the higher the temperature is, the lower the viscosity of siloxane is, the easier the siloxane is to be mixed with the filler uniformly, but the higher the temperature is, the lower the bulk density of the filler is, the difficult mixing is caused, and the uneven mixing is caused.
The granulation may be performed by any one of the following methods: hot grain cutting of air-cooled die surface, hot grain cutting of water-ring die surface, grain cutting of water-cooled brace, grain cutting of air-cooled brace, hot grain cutting of eccentric water mist and hot grain cutting of die surface under water.
The invention also provides polysiloxane particles without organic carriers, which are prepared by the preparation method.
The invention is further illustrated by the following specific examples:
it should be noted that: the proportions of the components of the following examples and comparative examples are by weight.
Example 1
A method for preparing silicone particles without organic carrier, comprising the steps of:
s1, setting the viscosity to be 5 multiplied by 106100 parts of linear polysiloxane with mPa.S and 0.12 percent of vinyl content and 180m of specific surface area210 portions of precipitation-method superfine white carbon black, 0.005 portion of hydrogen-containing siloxane with the hydrogen content of 0.35 percent and 1 portion of Pt-containing catalyst A with the Pt content of 500ppm are reacted and mixed for 2 hours in an internal mixer at 150 ℃ to prepare the high-viscosity polysiloxane composition A;
s2, mixing the high-viscosity polysiloxane composition A prepared in the step S1 with 50 parts of silane coupling agent surface-treated specific surface area of 180m2Adding/g of precipitation-process silicon dioxide into a kneader and mixing for 3 hours at 150 ℃; and then feeding the mixed material into a reciprocating single-screw extruder through a double cone to extrude at 150 ℃, and granulating and molding in a hot granulating mode through an air cooling die surface to prepare the polysiloxane particles SK-1.
Example 2
A process for the preparation of silicone particles without organic carrier, differing from example 1 in that:
the white carbon black in the step S1 is replaced by modified white carbon black A, and the preparation method of the modified white carbon black A comprises the following steps: the specific surface area is 180m2100 parts of precipitation-method ultrafine white carbon black and 3 parts of vinyltrimethoxysilane are kneaded in a kneading machine at 150 ℃.
The polysiloxane particles prepared in step S2 of this example were identified as SK-2.
Example 3
A process for the preparation of silicone particles without organic carrier, differing from example 1 in that:
replacing the white carbon black in the step S1 with modified white carbon black B, wherein the preparation method of the modified white carbon black B comprises the following steps: the specific surface area is 180m2100 portions of precipitation-method ultrafine white carbon black, 3 portions of vinyl trimethoxy silane and 0.01 portion of catalyst sulfuric acid are kneaded in a kneading machine at 150 ℃.
The polysiloxane particles prepared in step S2 of this example were identified as SK-3.
Example 4
A process for the preparation of silicone particles without organic carrier, differing from example 1 in that:
the white carbon black in the step S1 is replaced by modified white carbon black C, and the preparation method of the modified white carbon black C comprises the following steps: the specific surface area is 180m2100 portions of precipitation-method superfine white carbon black, 10 portions of vinyl triethoxysilane and 0.1 portion of catalyst sodium hydroxide are kneaded in a kneader at 150 ℃.
The polysiloxane particles prepared in step S2 of this example were designated SK-4.
Example 5
A process for the preparation of silicone particles without organic carrier, differing from example 1 in that:
the white carbon black in the step S1 is replaced by modified white carbon black D, and the preparation method of the modified white carbon black D comprises the following steps: the specific surface area is 180m 2100 portions of gas phase method superfine white carbon black per gram, 1 portion of vinyl tri-tert-butoxy silane and 0.001 portion of catalyst organic amine are kneaded in a kneader at 150 ℃.
The polysiloxane particles produced in step S2 of this example were identified as SK-5.
Example 6
A process for the preparation of silicone particles without organic carrier, differing from example 3 in that:
in step S2, the kneader is mixed for 5h at a temperature of 200 ℃; the extrusion temperature of the extruder was 200 ℃.
The polysiloxane particles prepared in step S2 of this example were identified as SK-6.
Example 7
A method for preparing silicone particles without organic carrier, comprising the steps of:
s1, reacting and mixing 100 parts of linear polysiloxane with the viscosity of 1 x 10^6 mPa.S and the vinyl content of 0.02%, 4 parts of modified white carbon black B, 0.01 part of hydrogen-containing siloxane with the hydrogen content of 0.08% and 0.1 part of Pt-containing catalyst A with the Pt content of 1000ppm in an internal mixer at 150 ℃ for 2 hours to prepare a high-viscosity polysiloxane composition B;
s2, mixing the high-viscosity polysiloxane composition B prepared in the step S1 with 80 parts of titanate coupling agent surface-modified specific surface area of 50m2Adding talcum powder/g into a kneading machine, and mixing at 150 ℃ for 3 h; and then feeding the mixed material into a reciprocating single-screw extruder through a double cone to extrude at 150 ℃, and granulating and molding in a hot granulating mode through an air cooling die surface to prepare polysiloxane particles SK-7.
Example 8
A method for preparing silicone particles without organic carrier, comprising the steps of:
s1, reacting and mixing 100 parts of linear polysiloxane with the viscosity of 1 x 10^7 mPa.S and the vinyl content of 0.2%, 20 parts of modified white carbon black B, 0.10 part of hydrogen-containing siloxane with the hydrogen content of 0.08% and 5 parts of Pt-containing catalyst A with the Pt content of 800ppm in an internal mixer at 150 ℃ for 2 hours to prepare a high-viscosity polysiloxane composition C;
s2, mixing the high-viscosity polysiloxane composition C prepared in the step S1 with 20 parts of aluminate coupling agent subjected to surface modification treatment and having a specific surface area of 200m2Adding/g of fumed silica into a kneader and mixing for 3h at 150 ℃; and then feeding the mixed material into a reciprocating single-screw extruder through a double cone to extrude at 150 ℃, and granulating and molding in a hot granulating mode through an air cooling die surface to prepare polysiloxane particles SK-8.
Comparative example 1
The comparative example provides a process for the preparation of silicone particles without organic carrier, characterized in that it comprises the following steps: will stick toDegree of 5X 106110 parts of linear polysiloxane mPaS with vinyl content of 0.12 percent and 50 parts of linear polysiloxane surface-treated by silane coupling agent and with specific surface area of 180m2Adding/g of precipitation-process silicon dioxide into a kneader and mixing for 3 hours at 150 ℃; and then, extruding the mixed material by a double-cone feeding reciprocating single-screw extruder at 150 ℃, and granulating and molding in an air-cooled die surface hot granulating mode to prepare the polysiloxane particles CK-1.
Comparative example 2
The invention provides a preparation method of polysiloxane particles containing an organic carrier, which comprises the steps of selecting polysiloxane with the weight average molecular weight of 60-70 ten thousand, the needle penetration of 200-240 and the viscosity of (6-8). times.10 ^6 mPa.S, and granulating and molding the polysiloxane particles and LLDPE (linear low-density polyethylene) in a weight ratio of 1:1 at the temperature of 150-170 ℃ through a double screw, wherein the prepared polysiloxane particles are marked as MB 1.
Test example 1: granulation Properties
Observing the granulation processes for preparing silicone particles of examples 1-8 and comparative example 1 and the properties of the silicone particles prepared thereby, the granulation properties and particle properties of the silicone particles prepared in each of the examples and comparative examples are shown in table 1:
TABLE 1 pelletization Properties and properties of the polysiloxane pellets prepared in the examples and comparative examples
From the results of table 1, it can be seen that:
from the results of comparative examples 1 to 8 and the results of comparative example 1, it can be seen that: by adopting the method of the invention to modify the polysiloxane, the polysiloxane is prepared into the polysiloxane composition with high viscosity, then the filler is added for granulation, the hardness of the polysiloxane can be greatly improved, the granulation can be smoothly carried out without adding an organic carrier, and the prepared polysiloxane has uniform particles, high hardness, regular surface and convenient packaging and transportation.
The results of comparative examples 1 and 2 and examples 3 to 8 show that after vinyl is grafted on the surface of white carbon black, the white carbon black and polysiloxane are more stably combined and are more uniformly dispersed, the promotion effect on the chain extension of polysiloxane is stronger, the obtained polysiloxane composition has higher viscosity and is easier to granulate, and the results of comparative examples 2 and 3 further show that in the process of grafting vinyl by white carbon black, the addition of a catalyst can promote better grafting of vinyl on the surface of white carbon black.
Test example 2: rheological Properties
In the test example, 10 sets of comparative tests are set, the raw materials of each test set are weighed according to the proportion shown in table 2 except for the selection of polysiloxane particles, the raw materials are weighed and then put into an internal mixer for internal mixing, and then the raw materials are added into a capillary extrusion device of a torque rheometer (the length-diameter ratio of a neck ring mold is 30:1, the temperature is 160 ℃) to test the rheological property; the choice of polysiloxane particles for each test group is shown in table 3. The results of the rheological measurements for each test group are shown in table 4.
TABLE 2 proportions of the raw materials added to the internal mixer
| Raw materials | EVA | LLDPE | MAH～LLDPE | Al(OH)3 | Mg(OH)2 | Polysiloxane particles |
| Proportioning | 30 | 5 | 5 | 45 | 15 | - |
TABLE 3 selection of the polysiloxane particles of the test groups
Table 4 evaluation of rheological properties of the test groups
From the test results of table 4, it can be seen that:
by comparing the results of test groups 1 to 8 with the result of test group 10, it can be seen that: the rheological property of the thermoplastic high-filler filled plastic product prepared by using the polysiloxane particles prepared by modifying the polysiloxane as the lubricant by adopting the method is superior to that of the thermoplastic plastic product prepared by using the existing silicone master batch containing the organic carrier as the lubricant, and the lubricating property of the polysiloxane particles without the organic carrier prepared by adopting the method is excellent.
By comparing the results of test groups 1 to 8 with the result of test group 9, it can be known that the polysiloxane particles obtained by modifying the polysiloxane surface grafted white carbon black have better lubricating efficiency when being added into resin as a lubricant; in addition, the data of the comparative test groups 1-2 and 3-8 show that the lubricating efficiency of the prepared polysiloxane particles is higher after the grafted polyethylene on the surface of the white carbon black is modified, than that of the test groups which are not modified by the grafted polyethylene on the white carbon black and have poor modifying effect on the grafted polyethylene.
Test example 3: scratch resistance and migration test
In this test example, 10 sets of comparative tests were carried out, and the polysiloxane particles prepared in examples 1 to 8 and comparative examples 1 to 2 were respectively added to a PP/POE/talc powder (weight ratio 71:8:20) system and injection molded into a 2mm thick plate for scratch resistance (popular PV3952, the smaller the Δ L value, the better the scratch resistance) and migration test (PV1306, 6 cycles, 96 h/cycle), and the results are shown in Table 5.
TABLE 5 scratch resistance and migration test results for each test set
From the test results of table 5, it can be seen that:
the silicone particles of test groups 1 to 8 have relatively good scratch resistance and good migration resistance, in particular the silicone particles of test groups 3 to 8 do not exhibit stickiness during the entire stickiness test; indicating that no significant migration or bleeding of the organopolysiloxane particles prepared according to the invention occurred.
Test example 4: gloss and coefficient of friction
In this test example, 10 sets of comparative tests were conducted, and the polysiloxane pellets obtained in examples 1 to 8 and comparative examples 1 to 2 were added to high density polyethylene (6094) respectively, and the mixture was uniformly mixed in an amount of 2.5%, extruded into a sheet by a torque rheometer single-screw extruder, and then tabletted and cooled on two rods to prepare a 2mm sheet. The gloss was measured with a gloss meter and the coefficient of static and dynamic friction was measured with a coefficient of friction meter, the data obtained are shown in table 6.
TABLE 6 gloss and coefficient of friction for each test group
From the test results of table 6, it can be seen that:
the gloss data for test groups 1-8 and 9-10 are almost indistinguishable, indicating that the organopolysiloxane particles prepared according to the invention have no effect on gloss.
The friction coefficients of the test groups 1 to 8 are smaller than the friction coefficients of the test groups 9 to 10, and the abrasion resistance coefficients of the test groups 3 to 8 are smaller than the abrasion resistance coefficients of the test groups 1 to 2, which shows that the dynamic and static friction coefficients of the system are small due to the organic carrier-free polysiloxane particles prepared by the invention, and particularly, the dynamic and static friction coefficients of the system are smaller due to the organic carrier-free polysiloxane particles which are grafted on the surface of polysiloxane after the white carbon black is modified in the preparation process.
In conclusion, the preparation method can smoothly prepare the polysiloxane particles without the organic carrier, the prepared polysiloxane particles without the organic carrier are uniform, high in hardness and regular in surface, and the rheological property, the wear resistance, the scratch resistance and the like of the resin are obviously improved when the polysiloxane particles without the organic carrier are applied to the processing process of the resin.
Claims (10)
1. A method for preparing silicone particles without organic carrier, which is characterized by comprising the following steps:
s1, reacting and mixing polysiloxane, modified white carbon black, a grafting agent and a catalyst A in a kneading machine or an internal mixer to prepare a high-viscosity polysiloxane composition; the molar fraction of vinyl chain links in the polysiloxane is 0.02-0.2%; the modified white carbon black is prepared by mixing and reacting raw materials including common white carbon black, a silane coupling agent containing vinyl and a catalyst B; the grafting agent is selected from any one of hydrogen-containing silicone oil containing at least 2 Si-H bonds, and the hydrogen content is 0.01-0.80 wt%;
S2, uniformly mixing the high-viscosity polysiloxane composition prepared in the step S1 with a filler, extruding and granulating to prepare the organic carrier-free polysiloxane particles.
2. Process for the preparation of silicone particles without organic carrier according to claim 1, characterized in that the silicone is chosen from those having a viscosity of 106～107Linear polysiloxanes of mPas.
3. The method for preparing polysiloxane particles without organic carrier according to claim 1, wherein in step S1, the ordinary silica includes one or both of silica prepared by gas phase method or precipitation method.
4. The method for preparing polysiloxane particles without organic carrier according to claim 3, wherein in step S1, the modified silica white is prepared by mixing and reacting raw materials comprising 100 parts of common silica white, 1-10 parts of silane coupling agent containing vinyl and 0.001-0.1 part of catalyst B.
5. The method for preparing polysiloxane particles without organic carrier according to claim 1, wherein in step S1, the catalyst a is selected from Pt, Rh, Ni, Co and compounds or complexes thereof; the grafting agent is any one of hydrogen-containing silicone oil containing at least 2 Si-H bonds, and the hydrogen content is 0.01-0.80 wt%.
6. The method for preparing organopolysiloxane particles without organic carrier according to claim 1, wherein in step S1, the weight ratio of each raw material satisfies: 100 parts of polysiloxane, 4-20 parts of white carbon black, 0.001-0.10 part of grafting agent and 0.01-100 parts of catalyst A.
7. The method for preparing polysiloxane particles without organic carrier according to claim 1, wherein in step S2, the filler is selected from a common filler or a modified filler; the modified filler is prepared by treating a common filler with a surface treating agent; the surface treating agent is selected from one or more of silane coupling agent, titanate coupling agent or aluminate coupling agent.
8. The method for preparing silicone particles without organic carrier according to claim 1, wherein in step S2, the weight ratio of the high viscosity silicone composition to the filler satisfies: 100: 20-80.
9. The method for preparing silicone particles without organic carrier according to claim 1, wherein in step S2, the high viscosity silicone composition and the filler are first added into an internal mixer or kneader and mixed for 0.5h to 6h at 50 to 200 ℃; and then feeding the mixed materials into a reciprocating single-screw extruder or a double-screw extruder through a double cone, extruding at 50-200 ℃, and granulating by a granulating device.
10. Organopolysiloxane particles free of organic carriers, which are produced by the method according to any one of claims 1 to 9.
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