WO2019178876A1 - Adhésif organosilicié sensible à la pression et son procédé de préparation - Google Patents

Adhésif organosilicié sensible à la pression et son procédé de préparation Download PDF

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Publication number
WO2019178876A1
WO2019178876A1 PCT/CN2018/080364 CN2018080364W WO2019178876A1 WO 2019178876 A1 WO2019178876 A1 WO 2019178876A1 CN 2018080364 W CN2018080364 W CN 2018080364W WO 2019178876 A1 WO2019178876 A1 WO 2019178876A1
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WO
WIPO (PCT)
Prior art keywords
sensitive adhesive
fluorine
silicone resin
containing phenyl
hours
Prior art date
Application number
PCT/CN2018/080364
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English (en)
Chinese (zh)
Inventor
李战雄
孙弋
纵亚坤
Original Assignee
南通纺织丝绸产业技术研究院
苏州大学
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Application filed by 南通纺织丝绸产业技术研究院, 苏州大学 filed Critical 南通纺织丝绸产业技术研究院
Priority to PCT/CN2018/080364 priority Critical patent/WO2019178876A1/fr
Publication of WO2019178876A1 publication Critical patent/WO2019178876A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • 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
    • C09J183/00—Adhesives based on 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; Adhesives based on derivatives of such polymers
    • C09J183/10—Block or graft copolymers containing polysiloxane sequences

Definitions

  • the invention relates to a high temperature resistant silicone pressure sensitive adhesive and a preparation method thereof, and belongs to the field of preparation of organic silicon materials and adhesives.
  • the active ingredient of the silicone pressure-sensitive adhesive is a product of a polycondensation reaction of a silicone resin and a silicone rubber (also known as a 107 rubber), which is diluted to a certain solid content by adding an organic solvent, and a crosslinking agent and other additives are added to obtain a product.
  • silicone rubber also known as a 107 rubber
  • the main role of silicone rubber is to give the pressure-sensitive adhesive the necessary cohesion.
  • the 107 glue commonly used in the synthesis of silicone pressure-sensitive adhesive has a number average molecular weight of 100,000 to 500,000, which is generally colorless and transparent at room temperature. Extremely viscous liquid or semi-solid; the silicone resin contains a polar silanol group in its molecular structure, providing wetting, initial tack and peel strength to the pressure sensitive adhesive.
  • silicone resin for preparing pressure sensitive adhesives is methyl silicone resin (referred to as MQ resin), which has the advantages of low raw material cost and good process performance.
  • MQ resin methyl silicone resin
  • silicone pressure-sensitive adhesives synthesized from methyl silicone resin have poor heat resistance, and such pressure-sensitive adhesives may fail when used for a long period of time at temperatures exceeding 300 ° C due to methyl silicon in the adhesive macromolecule.
  • the organic groups such as the base are thermally decomposed to increase the degree of cross-linking of the adhesive.
  • phenyl silicone resin instead of methyl silicone resin has a slightly better heat resistance, but debonding and brittleness occur after long-term use under ultra-high temperature conditions higher than 300 °C.
  • the invention aims at the current situation of insufficient high temperature resistance of the existing silicone pressure sensitive adhesive, and provides a fluorine-containing high temperature resistant silicone pressure sensitive adhesive, and a high temperature molecular pressure of the fluorine-containing phenyl silicone resin and the high molecular weight 107 to prepare a high temperature resistant pressure.
  • the method of the sensitive adhesive, the disclosed silicone pressure-sensitive adhesive has the characteristics of high temperature resistance and even high temperature resistance.
  • a silicone pressure sensitive adhesive whose chemical structural formula is as follows:
  • the preparation method of the above silicone pressure sensitive adhesive comprises the following steps:
  • the mass ratio of the activator, 107 peptizer, catalyst, and fluorophenyl silicone resin is (0.005-0.05): 1: (0.005-0.06): (1-10); the polycondensation product
  • the mass ratio to the curing agent is (0.02 to 0.5): (0.02 to 0.3).
  • the solvent in the activator solution is an aromatic hydrocarbon solvent
  • the solvent in the 107 gum solution is an aromatic hydrocarbon solvent
  • the solvent in the fluorine-containing phenyl silicone resin solution is an aromatic hydrocarbon solvent
  • the curing agent is hexamethyldisilazane
  • the catalyst is dibutyltin dilaurate
  • the activator is dimethyldimethoxysilane or dimethyldiethoxysilane .
  • step (1) the catalyst is added to the 107 gum solution at 80 ° C to 100 ° C; then, under the protection of nitrogen, the activator solution is added dropwise, and the reaction is kept for 1 to 6 hours after the completion of the dropwise addition; Adding a fluorophenyl silicone resin solution, and refluxing at 100 to 140 ° C for 2 to 60 hours to obtain a polycondensation product;
  • the temperature of the heat preservation and curing is 100 to 140 ° C, and the time is 1 to 6 hours.
  • the time for adding the activator solution is 0.5 to 3 hours.
  • the preparation method of the fluorine-containing phenyl silicone resin comprises the following steps:
  • the mass ratio of pentafluorostyrene, noble metal salt and methyldichlorosilane is 1: (0.003 to 0.006): (0.5 to 2); pentafluorophenethyldimethylchlorosilane and orthosilicate
  • pentafluorophenethyldimethylchlorosilane and orthosilicate In the mixture of ethyl esters, the mass ratio of pentafluorophenethyldimethylchlorosilane to ethyl orthosilicate is (1 to 6): (1 to 10); trihydrocarbyl monochlorosilane and ethyl orthosilicate
  • the mass ratio of trihydrocarbyl monochlorosilane to ethyl orthosilicate is (1 to 3): (1 to 10);
  • the noble metal salt is chloroplatinic acid; and the trihydrocarbyl monochlorosilane is trimethyl
  • the time of adding methyldichlorosilane is 0.5 to 5 hours; the time of adding the mixture of trihydrocarbylmonochlorosilane and ethyl orthosilicate is 0.5 to 1 hour; after the reaction of the step (1) is finished The reaction liquid is distilled off and distilled under reduced pressure to obtain pentafluorophenethyldimethylchlorosilane; after the step (2) is again subjected to polycondensation, the reaction liquid is subjected to cooling, vacuum distillation, liquid separation treatment, extraction, and distilled water washing. Drying, filtration, and distillation give a fluorine-containing phenyl silicone resin.
  • the invention also discloses the application of the fluorine-containing phenyl silicone resin in preparing the silicone pressure sensitive adhesive; the chemical structural formula of the fluorine-containing phenyl silicone resin is:
  • the chemical structural formula of the silicone pressure sensitive adhesive is as follows:
  • the aromatic hydrocarbon solvent of the present invention is a mixed solvent in which either or both of toluene and xylene are mixed in an arbitrary ratio; preferably, the reflux water separation time is from 2 to 60 hours, preferably from 12 to 24 hours.
  • reaction formula of the fluorophenyl silicone resin and the 107 rubber disclosed in the invention for synthesizing the silicone pressure sensitive adhesive by polycondensation reaction is as follows:
  • R -CH 3 or -CH 2 CH 3 .
  • the preparation process of the fluorophenyl silicone high temperature pressure sensitive adhesive comprises a polycondensation reaction and a post-treatment two-step reaction, which can be specifically as follows:
  • One part of 107 gum is dissolved in 0.5-10 parts of aromatic hydrocarbon solvent by weight, stirred and heated to 80 ° C ⁇ 100 ° C, and added 0.005 ⁇ 0.06 parts of dibutyl tin dilaurate (DBTL). Under nitrogen protection, add 0.005 ⁇ 0.05 parts of the activator dissolved in 0.1 ⁇ 0.5 parts of aromatic hydrocarbon solvent, add 0.5 ⁇ 3 hours, and keep the reaction for 1 ⁇ 6 hours after the addition. Then, adding 1 to 10 parts of a solution of fluorophenyl silicone resin dissolved in 1 to 10 parts of an aromatic hydrocarbon solvent, raising the temperature to 100 to 140 ° C, and refluxing the water for 2 to 60 hours;
  • DBTL dibutyl tin dilaurate
  • the preparation method of the fluorine-containing phenyl silicone resin of the present invention can be specifically as follows:
  • Mixed silane 1 ⁇ 3 parts of monochlorosilane monomer, 1 ⁇ 6 parts of pentafluorophenethyldimethylchlorosilane and 2 ⁇ 20 parts of ethyl orthosilicate are mixed by weight to obtain mixed silane;
  • Polycondensation reaction 1 to 5 parts of water and 0.5 to 2 parts of inorganic acid are dispersed in 1 to 20 parts of tetrahydrofuran by weight, and the temperature of the mixture is raised to 60 to 80 ° C by heating, and the above mixed silane is slowly added dropwise. Add 0.5 to 2 hours. After the addition is completed, the insulation reaction is continued for 1 to 6 hours;
  • Post-treatment After cooling the reaction liquid, the by-product ethanol and the solvent tetrahydrofuran were distilled off under reduced pressure, and the distillation temperature was 40 to 80 ° C, and the degree of vacuum was 0.5 to 20 mmHg.
  • the extracts were combined and washed 3 to 5 times with distilled water, using 1 to 5 portions of distilled water each time.
  • the silicone silicone resin Different from the traditional silicone pressure sensitive adhesive preparation, the silicone silicone resin, the vinyl silicone resin and the phenyl silicone resin are used.
  • the invention uses the pentafluorophenyl modified silicone resin as a raw material to prepare the silicone pressure sensitive adhesive. Has very good heat resistance.
  • the high temperature resistant silicone pressure sensitive adhesive provided by the invention is activated by adding an activator during the preparation of the adhesive, which can overcome the problem of poor reactivity of the extremely rigid pentafluorophenyl group introduced into the silicone resin;
  • the heat resistance of the adhesive is deteriorated, so that the adhesive is aged by adding hexamethyldisilazane before the end of the reaction.
  • the high temperature resistant silicone pressure sensitive adhesive provided by the invention has an easy ratio of fluorine-containing phenyl silicone resin and 107 rubber, and is convenient for preparing an adhesive suitable for different heat resistance requirements.
  • the raw materials used in the preparation of the fluorine-containing phenyl silicone pressure-sensitive adhesive of the invention are easy to obtain, the synthesis process is simple, and it is suitable for industrial production.
  • Figure 1 is a graph showing the thermal weight loss of the pressure sensitive adhesive of the present invention.
  • the performance detection steps of the present invention are as follows:
  • the bonding strength and heat aging resistance were tested according to GB/T 2792-1998 (pressure-sensitive adhesive 180° peel strength test method) and GB/T 17875-1999 (pressure-sensitive adhesive accelerated aging test method).
  • the invention uses a pentafluorophenyl silicone resin and a high molecular weight 107 glue as raw materials to synthesize a fluorine-containing phenyl silicone pressure sensitive adhesive by polycondensation reaction, and the product introduces a pentafluorophenyl modified silicone resin, which has a total of pentafluorophenyl groups.
  • the planar structure of the yoke and the fluorocarbon bond which is difficult to thermally debond the bond, the product has very excellent heat resistance.
  • the crosslinking agent used in the performance testing process is any one of dibenzoyl peroxide or peroxy-2,4-dichlorobenzoyl.
  • 80 g of water and 50 g of concentrated sulfuric acid were carefully and slowly introduced into 500 g of tetrahydrofuran, and after heating to raise the temperature of the mixture to 70 ° C, the above-prepared mixed silane was slowly added dropwise, and the dropping time was controlled at about 45 minutes. After the addition was completed, the reaction was continued for 6 hours. The reaction was stopped, and the reaction liquid was first distilled under reduced pressure to remove by-product ethanol and solvent tetrahydrofuran.
  • the distillation temperature was 60 ° C, the degree of vacuum was 10 mmHg, and distillation was carried out until no liquid was distilled off.
  • the toluene was extracted three times, and the amount of toluene used each time was 300 g.
  • the extracts were combined and washed 5 times with distilled water using 150 g of distilled water each time. After the end of the washing, it was further dried by adding 60 g of anhydrous sodium sulfate for 5 hours.
  • the desiccant was removed by filtration, and distilled under the conditions of a temperature of 80 ° C and a vacuum of 0.5 mmHg to obtain 380 g of a white loose solid product fluorophenyl silicone resin.
  • the polycondensation product was added with 12 g of hexamethyldisilazane and 4.6 g of isopropanol, and the mixture was aged for 5 hours. After the reaction is completed, the reaction is stopped, cooled, and discharged to obtain a high temperature resistant pressure sensitive adhesive. During the ripening process, a small amount of uncondensed silanol groups are further reacted.
  • the polycondensation product was added with 15 g of hexamethyldisilazane and 6.5 g of isopropanol, and the reaction was kept for 5 hours. After the reaction is completed, the reaction is stopped, cooled, and discharged to obtain a high temperature resistant pressure sensitive adhesive.
  • the molecular structure of the above pressure sensitive adhesive product is as follows:
  • the polycondensation product was added with 15 g of hexamethyldisilazane and 6.5 g of isopropanol, and the reaction was kept for 5 hours. After the reaction is completed, the reaction is stopped, cooled, and discharged to obtain a high temperature resistant pressure sensitive adhesive.
  • the polycondensation product was added with 15 g of hexamethyldisilazane and 6.5 g of isopropanol, and the reaction was kept for 5 hours. After the reaction is completed, the reaction is stopped, cooled, and discharged to obtain a high temperature resistant pressure sensitive adhesive.
  • Figure 1 is a graph of the above-mentioned pressure-sensitive adhesive thermal weight loss curve.
  • curve a is the thermogravimetric test result of the thermogravimetric test of the pressure sensitive adhesive prepared in the first embodiment
  • b is the thermogravimetric test result of the thermosensitive weight test of the pressure sensitive adhesive prepared in the second embodiment
  • c is the pressure prepared in the third embodiment.
  • the thermogravimetric test results of the thermosensitive rubber have a thermogravimetric curve
  • d is a thermogravimetric curve of the thermogravimetric test results of the pressure-sensitive adhesive prepared in Example 4. It can be seen that all pressure sensitive adhesives have good heat resistance. It can also be seen from the heat resistance test results that the pressure sensitive adhesive prepared by the present invention has good heat resistance, and the 10% weight loss temperature reaches 342 °C.
  • 80 g of toluene and 33 g of styrene were successively added, stirred and dissolved, and 0.16 g of a chloroplatinic acid catalyst was added under a nitrogen atmosphere.
  • the heating was turned on, and after heating to 80 ° C, 50 g of methyldichlorohydrosilane was added dropwise, and the dropping time was controlled to about 1 hour. After the completion of the dropwise addition, the reaction was kept for 2 hours.
  • 7 g of water and 6 g of concentrated sulfuric acid were carefully and slowly introduced into 55 g of tetrahydrofuran, and after heating to raise the temperature of the mixture to 72 ° C, the above-prepared mixed silane was slowly added dropwise, and the dropping time was controlled for 30 to 50 minutes. After the addition was completed, the reaction was continued for 6 hours. The reaction was stopped, and the reaction liquid was first distilled under reduced pressure to remove by-product ethanol and solvent tetrahydrofuran.
  • the distillation temperature was 60 ° C, the degree of vacuum was 10 mmHg, and distillation was carried out until no liquid was distilled off.
  • the toluene was extracted three times, and the amount of toluene used each time was 30 g.
  • the extracts were combined and washed 5 times with distilled water, using 15 g of distilled water each time. After the end of the washing, it was further dried by adding 5 g of anhydrous sodium sulfate for 6 hours.
  • the desiccant was removed by filtration, and distilled under the conditions of a temperature of 80 ° C and a vacuum of 0.5 mmHg to obtain 36 g of a white loose solid product phenethyl silicone resin.
  • DBTL dibutyltin dilaurate
  • the polycondensation product was added with 0.12 g of hexamethyldisilazane and 0.46 g of isopropyl alcohol, and the reaction was kept for 5 hours. After the reaction was over, the reaction was stopped, cooled, and discharged to obtain a control sample silicone pressure-sensitive adhesive.
  • control glue layer 0.05 ⁇ 0.06mm. After coating, it was dried at 90 ° C for 2 min and then dried at 150 ° C for 5 min.
  • the peel strength of phenyl silicone pressure sensitive adhesive was measured to be 30.8 N (2.5 cm).
  • accelerated aging test method of pressure sensitive adhesive the adhesive is resistant to compression and oxidation at 325 ° C for 72 h, 80% of the adhesive layer is peeled off after exposure at 260 ° C, and some adhesive layer remains on the metal surface, residual The glue layer becomes brittle, the color is white, the side is shrinking, and the pores appear.
  • the molecular structure of the control silicone pressure sensitive adhesive product is as follows:

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)

Abstract

L'invention concerne un adhésif organosilicié sensible à la pression et un procédé de préparation de celui-ci. L'adhésif organosilicié sensible à la pression est préparé par une réaction de polycondensation à l'aide de résine de silicone portant des groupes phényle contenant du fluor et de caoutchouc de silicone (caoutchouc de silicone 107) en tant que matière première. Etant donné qu'une certaine quantité d'un groupe phényle contenant du fluor est introduite dans la structure du produit, l'adhésif organosilicié sensible à la pression obtenu présente d'excellentes propriétés de résistance à haute température et d'adhérence et présente les avantages d'un procédé de préparation simple, de faibles exigences d'équipement et de caractère approprié pour la production en masse.
PCT/CN2018/080364 2018-03-23 2018-03-23 Adhésif organosilicié sensible à la pression et son procédé de préparation WO2019178876A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57140788A (en) * 1981-02-25 1982-08-31 Sagami Chem Res Center Preparation of vinylsilane having perfluoro group
CN103242798B (zh) * 2013-04-28 2015-01-21 深圳市新亚新材料有限公司 一种高透明单组份室温硫化硅橡胶及其制备方法
CN107674633A (zh) * 2017-11-02 2018-02-09 嘉善天胶装饰材料有限公司 一种镜底专用耐候胶及其制备方法
CN108373903A (zh) * 2018-03-13 2018-08-07 南通纺织丝绸产业技术研究院 耐高温压敏胶粘剂前驱体及其制备方法
CN108424746A (zh) * 2018-03-13 2018-08-21 苏州大学 有机硅压敏胶粘剂及其制备方法
CN108484914A (zh) * 2018-03-13 2018-09-04 苏州大学 氟硅树脂及其制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57140788A (en) * 1981-02-25 1982-08-31 Sagami Chem Res Center Preparation of vinylsilane having perfluoro group
CN103242798B (zh) * 2013-04-28 2015-01-21 深圳市新亚新材料有限公司 一种高透明单组份室温硫化硅橡胶及其制备方法
CN107674633A (zh) * 2017-11-02 2018-02-09 嘉善天胶装饰材料有限公司 一种镜底专用耐候胶及其制备方法
CN108373903A (zh) * 2018-03-13 2018-08-07 南通纺织丝绸产业技术研究院 耐高温压敏胶粘剂前驱体及其制备方法
CN108424746A (zh) * 2018-03-13 2018-08-21 苏州大学 有机硅压敏胶粘剂及其制备方法
CN108484914A (zh) * 2018-03-13 2018-09-04 苏州大学 氟硅树脂及其制备方法

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