CN109320723A - A kind of self-repair type organic siliconresin and preparation method thereof - Google Patents

A kind of self-repair type organic siliconresin and preparation method thereof Download PDF

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Publication number
CN109320723A
CN109320723A CN201811186227.4A CN201811186227A CN109320723A CN 109320723 A CN109320723 A CN 109320723A CN 201811186227 A CN201811186227 A CN 201811186227A CN 109320723 A CN109320723 A CN 109320723A
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polysiloxanes
self
organic siliconresin
type organic
repair type
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CN109320723B (en
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刘云鸿
彭新艳
刘云晖
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Guangdong Shierli New Materials Co.,Ltd.
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Quanzhou Three Glad Novel Material Science And Technology Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42Block-or graft-polymers containing polysiloxane sequences
    • C08G77/44Block-or graft-polymers containing polysiloxane sequences containing only polysiloxane sequences

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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)
  • Silicon Polymers (AREA)

Abstract

The invention discloses a kind of self-repair type organic siliconresins and preparation method thereof.The raw material of self-repair type organic siliconresin of the present invention specifically includes that the polysiloxanes of double bond sealing end, polysiloxanes, compatilizer, lipoic acid, the metallic compound of carboxy blocking etc..The polysiloxanes of polysiloxanes, carboxy blocking that the present invention is blocked by lipoic acid and double bond combines, and one-step method prepares the self-repair type organic siliconresin with self-repair function, and process is simple, is suitble to industrialized production;The present invention introduces the dynamic reversible covalent bond (cystine linkage) with reciprocal characteristics or the structural unit of reversible non-covalent key interaction (hydrogen bond and coordinate bond) in organosilicon chain, realizes the organosilicon material for providing and having multiple selfreparing multiple mechanism;Selfreparing organosilicon material of the present invention is during making and using, without using solvent, it is shown that good environmentally protective characteristic.

Description

A kind of self-repair type organic siliconresin and preparation method thereof
Technical field
The invention belongs to organic siliconresin and its preparation field, in particular to a kind of self-repair type organic siliconresin and its system Preparation Method.
Background technique
Organic siliconresin is poly- using Si-O-Si as the highly cross-linked type thermosetting property for connecting organic group on main chain, silicon atom Siloxane systems.The special the Nomenclature Composition and Structure of Complexes of silicone resin assigns its splendid heat resistance and weatherability, and have both excellent hydrophobic, The performances such as electrical isolation, anti-flammability, chemicals-resistant, radiation hardness, mould proof, anti-sticking demoulding.Its product relates generally to insullac, applies Material, adhesive, plastics, fire retardant, anti-blushing agent, micro mist and ladder polymer etc., in electronic apparatus, industry light industry textile industry, building, doctor The fields such as treatment, space flight have a wide range of applications.Silicone resin has many excellent performances, in many fields in occupation of irreplaceable Status.However, organosilicon material is still inevitably easy to be shortened it by extraneous mechanical damage during use Service life, and substantially increase the maintenance and alternative costs of material.And to solve the problems, such as this, there is organosilicon material certainly Repair ability is then a highly effective solution.
Currently, about the rare report of selfreparing organosilicon material.In general, introducing in macromolecular chain has reversible spy Property dynamic reversible covalent bond or reversible non-covalent key interaction structural unit, be building the high molecular main side of selfreparing Method.However, on the one hand, structural unit the drawing in macromolecular chain of dynamic reversible covalent bond or the interaction of reversible non-covalent key Enter, be typically necessary inside reaction system and cosolvent is added realizes, this will lead to selfreparing high molecular material in preparation and The release and energy consumption and environmental problem of volatilizable object (VOC) are brought in use process;On the other hand, existing selfreparing macromolecule material The selfreparing mechanism of material is relatively single, can not obtain the material for having both comprehensive performance well with ideal selfreparing effect.
Therefore it provides a kind of organic siliconresin with solvent-free environment-protection and multiple selfreparing mechanism, has important meaning Justice.
Summary of the invention
It is an object of the invention to: a kind of self-repair type organic siliconresin is provided.Self-repair type organic siliconresin of the present invention, Its raw material specifically includes that polysiloxanes, compatilizer, lipoic acid, the metallic compound of the polysiloxanes of double bond sealing end, carboxy blocking Deng.
Due in thiotic molecules five-membered ring the low bond energy of cystine linkage and reversible exchange dynamic equilibrium reaction, for realize this The self-repair function of invention organosilicon material provides possibility.The present invention is using cystine linkage-between mercaptan and cystine linkage itself Reversible exchange dynamic equilibrium reactivity worth, on the one hand, in a heated condition, the poly- silicon of (cystine linkage-thiol bond) and double bond sealing end Oxygen alkane reacts, and cystine linkage is introduced on silicone segments;On the other hand, control system lipoic acid content, in heating condition Under, dynamic exchange realization ring-opening polymerisation occurs for the cystine linkage in thiotic molecules five-membered ring, can be formed strong linear total containing double sulphur Valence skeleton structure;Thus it can get the organic siliconresin segment knot of the dynamic reversible covalent bond (cystine linkage) with reciprocal characteristics Structure.
The low bond energy of cystine linkage and reversible exchange dynamic equilibrium reaction are that Inventive polymers material is realized under temperate condition The selfreparing of material provides possibility, the polymer containing cystine linkage can under room temperature or environmental stimuli (such as visible light, ultraviolet light, Catalyst, alkaline environment, Redox Condition, heating) selfreparing is carried out to the crackle of appearance.
Due to containing carboxylic acid group in lipoic acid structure, to have the dynamic reversible covalent bond of reciprocal characteristics in system On the basis of, carboxylic acid structure is introduced on organic siliconresin side chain, pendant carboxylic acid group can be realized by hydrogen bond action to linear total The crosslinking of valence skeleton structure;In the presence of metal ion, carboxylic acid group can carry out complex reaction with metal ion, form coordinate bond Cross-linked structure;In addition, introducing the polysiloxanes containing carboxy blocking in system, on the one hand, the poly- silicon containing carboxy blocking can be passed through Carboxylic acid structure in the carboxyl of oxygen alkane and above-mentioned system on organic siliconresin side chain forms hydrogen bond action, realizes co-crosslinking;It is another Aspect, the carboxyl of the polysiloxanes containing carboxy blocking, can with metal ion carry out complex reaction, also can with it is organic in above-mentioned system Carboxylic acid collective effect on silicone resin side chain carries out complex reaction with metal ion, system coordination bond cross-linking structure is formed, to adjust Control the performance of resin.
The present invention introduces the dynamic reversible covalent bond (cystine linkage) with reciprocal characteristics in silicone resin system or can The structural unit of inverse non-covalent interaction (hydrogen bond and coordinate bond) realizes to provide have having for multiple selfreparing multiple mechanism Machine silicon materials.
Purpose to realize the present invention, a kind of self-repair type organic siliconresin, raw material include: in parts by weight
100 parts of polysiloxanes of double bond sealing end
0 ~ 100 part of the polysiloxanes of carboxy blocking
0 ~ 100 part of compatilizer
5 ~ 100 parts of lipoic acid
0.001 ~ 20 part of metallic compound
Wherein, the general formula of the polysiloxanes of the double bond sealing end are as follows:
Wherein, R1, R2 represent methyl or phenyl, and R1 is identical or different with R2;R3 represents linear two for having 0 to 6 carbon atoms Valence alkyl group or alkyl ether, R4 are double bond CH2=CH-;
The molecular weight of the polysiloxanes of the double bond sealing end is 600~50000;
The general formula of the polysiloxanes of the carboxy blocking are as follows:
Wherein, R1, R2 represent methyl or phenyl, and R1 is identical or different with R2;R3 represents linear two for having 0 to 6 carbon atoms Valence alkyl group or alkyl ether, R4 are carboxyl-COOH;
The molecular weight of the polysiloxanes of the carboxy blocking is 300~5000;
The compatilizer is diglycol diacrylate, triethylene-glycol diacrylate, isobomyl acrylate At least one of ester, tripropylene glycol diacrylate, divinylbenzene, styrene;The present invention uses compatilizer, on the one hand controllable System viscosity, so that system is more preferably uniformly mixed;On the other hand, reactive diluent contains double bond, may participate in the poly- of double bond sealing end The reaction of siloxanes and lipoic acid system regulates and controls the MOLECULE DESIGN and self-repair function of system, well reviews one's lessons by oneself to obtain The silicone resin material of multiple function.
The metallic compound is at least one of iron chloride, calcium chloride, zinc chloride, zinc acetate, zinc sulfate;
Another object of the present invention is to provide a kind of preparation methods of self-repair type organic siliconresin.
To realize this purpose, a kind of preparation method of self-repair type organic siliconresin, preparation step are as follows:
The polysiloxanes of double bond or carboxy blocking, compatilizer, lipoic acid room temperature are uniformly mixed in advance;It is heated to 60 ~ 120 DEG C Under the conditions of, it is stirred to react 5 ~ 300min, metallic compound is then added, reacts 1h;Then, subsequent vacuum defoamation, is reviewed one's lessons by oneself Replica organic siliconresin.
The polysiloxanes that is blocked compared with the prior art, the advantages of the present invention are as follows: the present invention by lipoic acid and double bond, The polysiloxanes of carboxy blocking combines, and one-step method prepares the self-repair type organic siliconresin with self-repair function, process work Skill is simple, is suitble to industrialized production;The present invention introduces dynamic reversible covalent bond (double sulphur with reciprocal characteristics in organosilicon chain Key) or reversible non-covalent key interaction (hydrogen bond and coordinate bond) structural unit, realize provide have multiple selfreparing it is compound The organosilicon material of mechanism;Selfreparing organosilicon material of the present invention is during making and using, without using solvent, it is shown that Good environmentally protective characteristic.
Detailed description of the invention
Fig. 1 is the selfreparing photo of embodiment self-repair type organic siliconresin.
Specific embodiment
Specific embodiments of the present invention will be described in further detail for son with reference to the accompanying drawings and examples, but this hair Bright embodiment is without being limited thereto.
Embodiment 1
By 100g end-vinyl poly- (dimethyl siloxane) (average molecular weight 1000), 20g α, ω-dicarboxyl poly dimethyl silicon Oxygen alkane (average molecular weight 1000), 20g diglycol diacrylate, 30g lipoic acid room temperature are uniformly mixed in advance; It is heated under the conditions of 90 DEG C, is stirred to react 100min, 0.3g iron chloride is then added, react 1h;Then, subsequent vacuum defoamation, Obtain self-repair type organic siliconresin.
Referring to attached drawing 1, it is the selfreparing photo of self-repair type organic siliconresin provided in this embodiment.Firstly, incite somebody to action this The self-repair type organic siliconresin that embodiment obtains is cut into two pieces, then places the self-repair type organic siliconresin after cutting Self-repair type organic siliconresin is combined together after carrying out micro- squeeze to two pieces of cuttings together, until crack disappears.The results show that Micro- extruding about 10min is carried out under the conditions of 40 DEG C, self-repair type organic siliconresin heals together after two pieces of cuttings, and selfreparing The mechanical property of type organic siliconresin is kept approximately constant before and after reparation.
Embodiment 2
By 100g end-vinyl poly- (dimethyl siloxane) (average molecular weight 2000), 40g divinylbenzene, 10g lipoic acid room Temperature is uniformly mixed in advance;It is heated under the conditions of 80 DEG C, is stirred to react 100min, 0.8g iron chloride is then added, react 1h;With Afterwards, subsequent vacuum defoamation obtains self-repair type organic siliconresin.
Referring to 1 selfreparing view mode of embodiment, self-repair type organic siliconresin provided in this embodiment can be in 50 DEG C of items Self-repair function is realized under part, and the mechanical property of organic siliconresin is kept approximately constant before and after reparation.
Embodiment 3
By 100g end-vinyl poly- (dimethyl siloxane) (average molecular weight 5000), 100g α, ω-dicarboxyl polymethyl-benzene Radical siloxane (average molecular weight 1000), 80g triethylene-glycol diacrylate, 5g lipoic acid room temperature are stirred in advance It is even;It is heated under the conditions of 90 DEG C, is stirred to react 100min, 0.05g iron chloride is then added, react 1h;Then, subsequent vacuum is de- Bubble, obtains self-repair type organic siliconresin.
Referring to 1 selfreparing view mode of embodiment, self-repair type organic siliconresin provided in this embodiment can be in 60 DEG C of items Self-repair function is realized under part, and the mechanical property of organic siliconresin is kept approximately constant before and after reparation.
Embodiment 4
By 100g end-vinyl poly- (dimethyl siloxane) (average molecular weight 600), 5g α, ω-dicarboxyethyl poly dimethyl Siloxanes (average molecular weight 5000), 10g isobornyl acrylate, 100g lipoic acid room temperature are uniformly mixed in advance;Heating To under the conditions of 100 DEG C, it is stirred to react 80min, 0.5g zinc sulfate is then added, reacts 1h;Then, subsequent vacuum defoamation, obtains Self-repair type organic siliconresin.
Referring to 1 selfreparing view mode of embodiment, self-repair type organic siliconresin provided in this embodiment can be in 40 DEG C of items Self-repair function is realized under part, and the mechanical property of organic siliconresin is kept approximately constant before and after reparation.
Embodiment 5
By 100g ethenyl blocking methyl phenyl silicone (average molecular weight 50000), 10g α, ω-dicarboxypropyl is poly- Dimethyl siloxane (average molecular weight 300), 60g tripropylene glycol diacrylate, 40g lipoic acid room temperature are stirred in advance It is even;It is heated under the conditions of 90 DEG C, is stirred to react 200min, 2g zinc acetate is then added, react 1h;Then, subsequent vacuum defoamation, Obtain self-repair type organic siliconresin.
Referring to 1 selfreparing view mode of embodiment, self-repair type organic siliconresin provided in this embodiment can be in 50 DEG C of items Self-repair function is realized under part, and the mechanical property of organic siliconresin is kept approximately constant before and after reparation.
Embodiment 6
By 100g ethenyl blocking methyl phenyl silicone (average molecular weight 10000), 30g α, the poly- diformazan of ω-dicarboxyl Radical siloxane (average molecular weight 2000), 30g divinylbenzene, 20g lipoic acid room temperature are uniformly mixed in advance;It is heated to 90 DEG C Under the conditions of, it is stirred to react 100min, 1g zinc chloride is then added, reacts 1h;Then, subsequent vacuum defoamation, obtains self-repair type Organic siliconresin.
Referring to 1 selfreparing view mode of embodiment, self-repair type organic siliconresin provided in this embodiment can be in room temperature item Self-repair function is realized under part, and the mechanical property of organic siliconresin is kept approximately constant before and after reparation.
Embodiment 7
By 100g ethenyl blocking methyl phenyl silicone (average molecular weight 8000), 60g α, ω-dicarboxyl poly dimethyl Siloxanes (average molecular weight 800), 100g divinylbenzene, 30g lipoic acid room temperature are uniformly mixed in advance;It is heated to 120 DEG C Under the conditions of, it is stirred to react 5min, 0.001g calcium chloride is then added, reacts 1h;Then, subsequent vacuum defoamation, obtains selfreparing Type organic siliconresin.
Referring to 1 selfreparing view mode of embodiment, self-repair type organic siliconresin provided in this embodiment can be in 45 DEG C of items Self-repair function is realized under part, and the mechanical property of organic siliconresin is kept approximately constant before and after reparation.
Embodiment 8
By 100g ethenyl blocking methyl phenyl silicone (average molecular weight 1000), 25g α, ω-dicarboxyl poly dimethyl Siloxanes (average molecular weight 1200), 80g lipoic acid room temperature are uniformly mixed in advance;It is heated under the conditions of 60 DEG C, stirring is anti- 300min is answered, 20g iron chloride is then added, reacts 1h;Then, subsequent vacuum defoamation obtains self-repair type organic siliconresin.
Referring to 1 selfreparing view mode of embodiment, self-repair type organic siliconresin provided in this embodiment can be in 60 DEG C of items Self-repair function is realized under part, and the mechanical property of organic siliconresin is kept approximately constant before and after reparation.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.

Claims (2)

1. a kind of self-repair type organic siliconresin, which is characterized in that raw material includes: in parts by weight
100 parts of polysiloxanes of double bond sealing end
0 ~ 100 part of the polysiloxanes of carboxy blocking
0 ~ 100 part of compatilizer
5 ~ 100 parts of lipoic acid
0.001 ~ 20 part of metallic compound
Wherein, the general formula of the polysiloxanes of the double bond sealing end are as follows:
Wherein, R1, R2 represent methyl or phenyl, and R1 is identical or different with R2;R3 represents linear two for having 0 to 6 carbon atoms Valence alkyl group or alkyl ether, R4 are carbon-carbon double bond CH2=CH-;
The molecular weight of the polysiloxanes of the double bond sealing end is 600~50000;
The general formula of the polysiloxanes of the carboxy blocking are as follows:
Wherein, R1, R2 represent methyl or phenyl, and R1 is identical or different with R2;R3 represents linear two for having 0 to 6 carbon atoms Valence
Alkyl group or alkyl ether, R4 are carboxyl-COOH;
The molecular weight of the polysiloxanes of the carboxy blocking is 300~5000;
The compatilizer is diglycol diacrylate, triethylene-glycol diacrylate, isobomyl acrylate At least one of ester, tripropylene glycol diacrylate, divinylbenzene, styrene;
The metallic compound is at least one of iron chloride, calcium chloride, zinc chloride, zinc acetate, zinc sulfate.
2. a kind of preparation method of self-repair type organic siliconresin as described in claim 1, it is characterised in that: preparation step Are as follows:
The polysiloxanes of double bond sealing end, the polysiloxanes of carboxy blocking, compatilizer, lipoic acid room temperature are uniformly mixed in advance; It is heated under the conditions of 60 ~ 120 DEG C, is stirred to react 5 ~ 300min, metallic compound is then added, react 1h;Subsequent vacuum defoamation, Obtain self-repair type organic siliconresin.
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CN111154141A (en) * 2020-01-21 2020-05-15 汕头市骏码凯撒有限公司 Heat-resistant agent and preparation method thereof
CN111454606A (en) * 2020-05-14 2020-07-28 深圳市华星光电半导体显示技术有限公司 Perovskite ink, liquid crystal display panel and O L ED display panel
CN112375162A (en) * 2020-10-26 2021-02-19 贵州大学 Preparation method of styrene butadiene rubber based on self-repairing function
CN112521754A (en) * 2020-10-30 2021-03-19 广东工业大学 MXene nanosheet compounded heat-conducting gel with thermal self-repairing performance and preparation method thereof

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CN109749086A (en) * 2019-02-22 2019-05-14 青岛科技大学 A kind of selfreparing elastomer silicone and preparation method thereof based on dynamic cystine linkage
CN111154141A (en) * 2020-01-21 2020-05-15 汕头市骏码凯撒有限公司 Heat-resistant agent and preparation method thereof
CN111454606A (en) * 2020-05-14 2020-07-28 深圳市华星光电半导体显示技术有限公司 Perovskite ink, liquid crystal display panel and O L ED display panel
CN112375162A (en) * 2020-10-26 2021-02-19 贵州大学 Preparation method of styrene butadiene rubber based on self-repairing function
CN112375162B (en) * 2020-10-26 2022-11-01 贵州大学 Preparation method of styrene butadiene rubber based on self-repairing function
CN112521754A (en) * 2020-10-30 2021-03-19 广东工业大学 MXene nanosheet compounded heat-conducting gel with thermal self-repairing performance and preparation method thereof

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