CN113527691A - Fluorosilicone polymer and preparation method thereof - Google Patents
Fluorosilicone polymer and preparation method thereof Download PDFInfo
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- CN113527691A CN113527691A CN202110704101.7A CN202110704101A CN113527691A CN 113527691 A CN113527691 A CN 113527691A CN 202110704101 A CN202110704101 A CN 202110704101A CN 113527691 A CN113527691 A CN 113527691A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/44—Block-or graft-polymers containing polysiloxane sequences containing only polysiloxane sequences
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/385—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing halogens
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
- C09J7/401—Adhesives in the form of films or foils characterised by release liners characterised by the release coating composition
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Abstract
The invention discloses a fluorine-silicon polymer and a preparation method thereof, wherein the preparation method comprises the following steps: weighing the following components in parts by weight: 100 parts of hydrogen-containing silicone oil, 0.1-1000 parts of fluorine-containing compound, 1-1000 parts of long-chain silicone oil, 0.001-10 parts of platinum catalyst and 0.001-10 parts of acid catalyst; mixing a fluorine-containing compound and a platinum catalyst to obtain a reaction solution A; mixing long-chain silicone oil and an acid catalyst to obtain a reaction solution B; introducing hydrogen-containing silicone oil and the reaction solution A into a first microreactor through different pipelines, adjusting the reaction temperature to 120-150 ℃, and fully reacting to obtain an intermediate product C; and (3) introducing the intermediate product C and the reaction solution B into a second microreactor through different pipelines, adjusting the reaction temperature to 150-170 ℃, and fully reacting to obtain the fluorosilicone polymer.
Description
Technical Field
The invention relates to the field of preparation of fluorine-silicon polymers, and particularly relates to a fluorine-silicon polymer and a preparation method thereof.
Background
The silicon polymer is known as an industrial material 'pearl on crown' by virtue of excellent heat resistance, weather resistance, oil resistance, wear resistance, corrosion resistance, high light transmittance, high flame retardance, low surface energy and low dielectric coefficient, is of great importance in the fields of aerospace, transportation, electronic circuits and the like, and is a special material with national strategic significance.
The traditional fluorine-silicon polymer mainly adopts two technical routes: hydrolysis and ring opening. The hydrolysis method is to obtain the fluorine-silicon polymer by adopting fluorine-silicon alkyl through the hydrolysis of chloride ions or methoxy and ethoxy. However, the method of preparation has two disadvantages: 1, generating a large amount of waste water after hydrolysis; 2, neutralizing after reaction to generate waste residues; 3, the molecular weight of the generated polymer is low, a large amount of ring bodies are formed, and the purity of the polymer is low. The ring-opening method is easy to generate rearrangement phenomenon in the synthesis process, namely, the ring body cannot be converted into the high molecular polymer, and the performance of the high molecular polymer is seriously influenced.
At present, most of fluorosilicone polymers are prepared by the two methods, and the application of products in the field of electronic circuits is in a bottleneck.
Disclosure of Invention
In order to overcome the above defects of the conventional organic silicon polymer coating, the first aspect of the present invention provides a preparation method of a fluorosilicone polymer, which comprises the following specific technical scheme:
a method for preparing a fluorosilicone polymer, comprising:
weighing the following components in parts by weight:
mixing a fluorine-containing compound and a platinum catalyst to obtain a reaction solution A;
mixing long-chain silicone oil and an acid catalyst to obtain a reaction solution B;
introducing hydrogen-containing silicone oil and the reaction solution A into a first microreactor through different pipelines, adjusting the reaction temperature to 120-150 ℃, and fully reacting to obtain an intermediate product C;
and (3) introducing the intermediate product C and the reaction solution B into a second microreactor through different pipelines, adjusting the reaction temperature to 150-170 ℃, and fully reacting to obtain the fluorosilicone polymer.
In some embodiments, the hydrogen content of the hydrogen-containing silicone oil is 1.2-1.6%.
In some embodiments, the fluorochemical compound has the structure:
wherein R is a spacer group, R is-O-, -S-, CnH2n-COO-, -CO-, R' is H or CH3T is-CnF2n+1Or a perfluoropolyether segment structure.
In some embodiments, the long chain silicone oil has the structure:
wherein X is H, CH3、-CH＝CH2OH and acrylate group, w is 0-1000, and y is 0-1000.
In some embodiments, the platinum catalyst is a cassett catalyst or a spiel catalyst.
In some embodiments, the acidic catalyst is one or more of hydrochloric acid, sulfuric acid, phosphoric acid, and heteropoly acids.
The invention also provides a fluorine-silicon polymer, which is prepared by the preparation method.
The fluorine-silicon polymer prepared by the invention is suitable for release protection of materials such as circuit boards, glass products, integrated circuit boards and the like, and can also be used as an auxiliary agent of paint.
Drawings
FIG. 1 is a process flow diagram of the preparation method of fluorosilicone polymer of the present invention,
Detailed Description
The present invention is described in detail below with reference to examples, and the description in this section is only exemplary and explanatory and should not be construed as limiting the scope of the present invention in any way.
It should be noted that the experimental methods used in the examples are all conventional methods unless otherwise specified, and the materials, reagents, and the like used in the examples are commercially available unless otherwise specified.
For example, the terminal side vinyl silicone oil in example 1 is RH terminal side vinyl silicone oil available from new chemical material ltd of rude bluegrass, zhejiang.
Example 1
Referring to fig. 1, the preparation process of the fluorosilicone polymer in this embodiment is as follows:
554 parts of perfluorohexylethylene and 0.01 part of a Karster catalyst were mixed to prepare a reaction solution A.
315 parts of terminal side vinyl silicone oil and 1 part of trifluoroacetic acid were mixed to obtain a reaction solution B.
100 parts of hydrogen-containing silicone oil and the reaction solution A are led into a first microreactor through different pipelines, the reaction temperature is 120 ℃, and an intermediate product C is obtained.
And (3) allowing the intermediate product C and the reaction solution B to flow into a second microreactor through different pipelines, wherein the reaction temperature is 150 ℃, and the obtained final product is a fluorosilicone polymer.
After diluting the fluorosilicone polymer with heptane to 80%, compared with a dow 7785 type fluorosilicone release agent, according to the following steps: 7560 crosslinking agent: platinum catalyst: dissolving heptane 100:3.2:0.6:1600, coating wire bar on corona PET film, baking at 150 deg.C for 120s to obtain fluorine release film, and attaching MY2G adhesive tape.
And (3) testing the release force: and (3) sticking a 25mm wide MY2G adhesive tape on the surface of the release film, rolling back and forth three times by using a compression roller, standing at room temperature at 70 ℃ for 24h, and testing on a tensile testing machine.
And (3) testing the adhesive force: and (3) attaching 25mm wide MY2G adhesive tape to a stainless dry plate, wherein the peel force is tested to be G1, attaching 25mm wide MY2G adhesive tape to a release film, aging in an oven at 70 ℃ for 24h, removing the release film, and attaching the release film to a stainless steel plate, wherein the peel force is tested to be G1, and the residual adhesion force is G2/G1-100%.
Example 2
Referring to fig. 1, the preparation process of the fluorosilicone polymer in this embodiment is as follows:
640 parts of dodecafluoroheptyl methacrylate and 0.1 part of Spirol catalyst were mixed to prepare a reaction solution A.
And mixing 520 parts of hydroxy dimethyl silicone oil and 1 part of triflic acid to obtain a reaction solution B.
100 parts of hydrogen-containing silicone oil and the reaction solution A are led into a first microreactor through different pipelines, the reaction temperature is 130 ℃, and an intermediate product C is obtained.
And (3) allowing the intermediate product C and the reaction solution B to flow into a second microreactor through different pipelines, wherein the reaction temperature is 160 ℃, and the obtained final product is a fluorosilicone polymer.
3M anticorrosive paint 1700(RM1) and anticorrosive paint 1700(RM2) added with 2% of fluorosilicone polymer are sprayed on a PCB, and the contact angle, the adhesive force (GB/T9286-88) and the shedding condition under the double 85(85 ℃/85% RH) condition are tested.
| Contact angle | Adhesion force | Double 85 test | |
| RM1 | 110° | 1 to 2 stages | Coating peeling off |
| RM2 | 120° | Level 0 | The coating layer does not fall off |
Example 3
Referring to fig. 1, the preparation process of the fluorosilicone polymer in this embodiment is as follows:
655 parts of methacrylate perfluoropolyether and 0.11 part of Karster catalyst were mixed to prepare a reaction solution A.
And mixing 60 parts of acrylate-terminated dimethyl silicone oil and 1 part of trifluoric acid to obtain a reaction solution B.
100 parts of hydrogen-containing silicone oil and the reaction solution A are led into a first microreactor through different pipelines, the reaction temperature is 140 ℃, and an intermediate product C is obtained.
And (3) allowing the intermediate product C and the reaction solution B to flow into a second microreactor through different pipelines, wherein the reaction temperature is 150 ℃, and the obtained final product is a fluorosilicone polymer.
Dissolving the fluorosilicone polymer in the UV photocuring polyurethane acrylate coating, and comparing the contact angle, the hand feeling smoothness, the adhesive force and other data before and after adding the fluorosilicone polymer.
The fluorine-silicon polymer prepared by the invention is suitable for release protection of materials such as circuit boards, glass products, integrated circuit boards and the like, and can also be used as an auxiliary agent of paint.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (7)
1. A preparation method of a fluorosilicone polymer is characterized by comprising the following steps:
weighing the following components in parts by weight:
mixing a fluorine-containing compound and a platinum catalyst to obtain a reaction solution A;
mixing long-chain silicone oil and an acid catalyst to obtain a reaction solution B;
introducing hydrogen-containing silicone oil and the reaction solution A into a first microreactor through different pipelines, adjusting the reaction temperature to 120-150 ℃, and fully reacting to obtain an intermediate product C;
and (3) introducing the intermediate product C and the reaction solution B into a second microreactor through different pipelines, adjusting the reaction temperature to 150-170 ℃, and fully reacting to obtain the fluorosilicone polymer.
2. The method for preparing a fluorosilicone polymer according to claim 1, wherein: the hydrogen content of the hydrogen-containing silicone oil is 1.2-1.6%.
3. The method for preparing a fluorosilicone polymer according to claim 1, wherein: the structure of the fluorine-containing compound is as follows:
wherein R is a spacer group, R is-O-, -S-, CnH2n-COO-, -CO-, R' is H or CH3T is-CnF2n+1Or perfluoropolyethersAnd (3) a chain segment structure.
4. The method for preparing a fluorosilicone polymer according to claim 1, wherein: the long-chain silicone oil has the following structure:
wherein X is H, CH3、-CH＝CH2OH and acrylate group, w is 0-1000, and y is 0-1000.
5. The method for preparing a fluorosilicone polymer according to claim 1, wherein: the platinum catalyst is a Karster catalyst or a Spire catalyst.
6. The method for preparing fluorosilicone polymer according to claim 1, wherein the acidic catalyst is one or more of hydrochloric acid, sulfuric acid, phosphoric acid and heteropoly acid.
7. A fluorosilicone polymer, characterized in that, said fluorosilicone polymer is prepared by the preparation method of any one of claims 1 to 6.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115434044A (en) * | 2022-11-07 | 2022-12-06 | 江苏恒力化纤股份有限公司 | Solvent-free bi-component spinning oil agent and preparation method and application thereof |
| CN116715855A (en) * | 2023-07-06 | 2023-09-08 | 深圳市金斯源电子商务有限公司 | Oleophobic skin feel handfeel agent and preparation method thereof |
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| CN115434044A (en) * | 2022-11-07 | 2022-12-06 | 江苏恒力化纤股份有限公司 | Solvent-free bi-component spinning oil agent and preparation method and application thereof |
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Application publication date: 20211022 |