阅读说明：本技术 一种用于制造热硫化硅胶加热器的复合材料及其制备方法 (Composite material for manufacturing heat vulcanized silica gel heater and preparation method thereof ) 是由 高旺 于 2021-09-06 设计创作，主要内容包括：本发明公开了一种用于制造热硫化硅胶加热器的复合材料及其制备方法,所述复合材料由上至下依次包括第一硫化硅胶层、镍铬合金层、第二硫化硅胶层和玻璃纤维布层,其中第二硫化硅胶层和玻璃纤维布层之间通过胶粘剂热压粘结。与现有技术相比,本发明的复合材料具有较优良的耐高温性,另外,玻璃纤维层与硫化硅胶层之间结合的附着力明显提高,阻燃效果好,导热效果突出,并且成本低廉,具有很好的应用前景。(The invention discloses a composite material for manufacturing a heat vulcanized silica gel heater and a preparation method thereof. Compared with the prior art, the composite material has excellent high temperature resistance, in addition, the adhesive force of the combination between the glass fiber layer and the vulcanized silica gel layer is obviously improved, the flame retardant effect is good, the heat conduction effect is outstanding, in addition, the cost is low, and the application prospect is good.)

1. The composite material for manufacturing the heat vulcanized silica gel heater is characterized by sequentially comprising a first silicon sulfide gel layer, a nickel-chromium alloy layer, a second silicon sulfide gel layer and a glass fiber cloth layer from top to bottom, wherein the second silicon sulfide gel layer and the glass fiber cloth layer are bonded through an adhesive in a hot pressing mode.

2. The composite material for manufacturing a heat-vulcanized silicone heater according to claim 1, wherein the adhesive comprises the following components in parts by weight: 60-90 parts of epoxy resin, 20-35 parts of polyester modified phenyl organosilicon, 5-10 parts of perfluoropolyether diol, 15-25 parts of epoxy diluent, 10-20 parts of epoxy curing agent, 5-10 parts of filler, 4-8 parts of melamine cyanurate and 0.5-2 parts of silane coupling agent.

3. The composite material for manufacturing a heat-vulcanized silicone heater according to claim 2, wherein the epoxy resin is one or more selected from the group consisting of aromatic epoxy resin, novolac epoxy resin, and alicyclic epoxy resin.

4. A composite material for use in the manufacture of a heat-vulcanized silicone heater according to claim 2, wherein said filler is selected from one or more of silica, calcium carbonate, alumina, silicon nitride, aluminum nitride or silicon carbide.

5. The composite material for manufacturing a heat-vulcanized silica gel heater according to claim 2, wherein the silane coupling agent is one or more selected from aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, γ -methacryloxypropyltrimethoxysilane, γ -aminopropylmethyldiethoxysilane, and methyltrimethoxysilane.

6. The composite material for use in the manufacture of a heat-vulcanized silicone heater according to claim 2, wherein said polyester-modified phenyl silicone has the following structure:

wherein a represents an integer of 0 to 50, b represents an integer of 10 to 50, and c represents an integer of 0 to 10;

R¹to representWherein, represents the grafting site of the group, and m represents an integer of 4 to 15.

7. The composite material for manufacturing a heat-vulcanized silicone heater according to claim 6, wherein the polyester-modified phenylsilicone is prepared by the following method:

(1) under the conditions of nitrogen environment, platinum catalysis and 60-120 ℃ of reaction temperature, phenyl hydrogen-containing silicone oil and ethylene glycol monoallyl ether are subjected to hydrosilylation reaction to generate an organosilane alcohol intermediate, and then excessive ethylene glycol monoallyl ether is removed under the vacuum condition of less than-0.095 MPa;

(2) under the conditions of nitrogen environment and reaction temperature of 80-130 ℃, the organosilicon alkyl alcohol intermediate and a certain amount of caprolactone are subjected to ring-opening esterification reaction under the action of an organic metal catalyst until the residue of the caprolactone is less than 0.5 percent.

8. The composite material for manufacturing a hot silica gel heater according to claim 7, wherein the organometallic catalyst in the step (2) is zirconium n-butoxide and the addition amount is 1-3% of the total amount of the charge.

9. A method of preparing a composite material for use in the manufacture of a heat-vulcanized silicone heater as claimed in any one of claims 1 to 8, comprising the steps of:

step (A): weighing epoxy resin, a polyhydroxy crosslinking agent, perfluoropolyether diol, an epoxy diluent, a filler, melamine cyanurate and a silane coupling agent according to a proportion, adding the epoxy resin, the polyhydroxy crosslinking agent, the perfluoropolyether diol, the epoxy diluent, the filler, the melamine cyanurate and the silane coupling agent into a stirrer to be dispersed and stirred at a high speed, adding an epoxy curing agent after the dispersion is uniform, and continuously stirring to prepare an adhesive for later use;

step (B): brushing the adhesive prepared in the step (A) on one side of the glass fiber cloth, then sequentially rolling the unvulcanized second silica gel layer, the nichrome heating component and the unvulcanized first silica gel layer to one side of the glass fiber cloth coated with the adhesive, and then putting the glass fiber cloth into a tunnel furnace for high-temperature vulcanization to form a composite structure of the glass fiber cloth layer, the second silica gel layer, the nichrome layer and the first silicon sulfide rubber layer.

10. The method for preparing a composite material for manufacturing a hot vulcanized silicone heater according to claim 9, wherein the surface temperature of the calender roller is controlled to be 5-15 ℃ during the calendering process, and the calendering is performed at a speed of 3-5 m/min; the temperature of the high-temperature vulcanization is 110-170 ℃.

Technical Field

The invention relates to the field of preparation of silica gel heaters, in particular to a composite material for manufacturing a heat vulcanized silica gel heater and a preparation method thereof.

Background

In industrial and agricultural production and general life, objects are required to be insulated or heated frequently, especially objects with irregular shapes, and a heating belt and a heater are good choices. The heaters commonly available in the market are generally classified into a silica gel heater, a PVC heater and a teflon heater according to different materials. Among them, teflon heaters are relatively more resistant to high temperatures, but the expensive price makes many users hard to bear; the PVC material is low in price, but cannot resist high temperature, the outer skin can be melted due to high temperature, and more manufacturers use recycled materials for production, so that the material which cannot resist high temperature is easier to melt, and the use risk of the PVC heater is higher; silica gel is a common high-temperature-resistant insulating material, the skin is soft and elastic, the working temperature is 60 ℃ below zero to 200 ℃, the price is low, reclaimed materials cannot be used for production, and the reliability is high, so that the silica gel is popular.

The silica gel heater is generally formed by laminating silica gel materials and electric heating film elements, in the using process, because the tensile strength is not enough, or the manufacturing process is unqualified, after the silica gel heater is used for a period of time, the problems of surface layer falling, electric leakage or poor heat conduction effect and the like can occur, so that great potential safety hazard can exist in the using process of the silica gel heater, the using time of the silica gel heater is limited, a lot of troubles can be caused to users, in order to ensure the using safety of equipment, the silica gel heater needs to be regularly detected, a large amount of manpower and energy are needed to be consumed, and therefore the existing silica gel heater cannot really meet the market demands, and the technology of the silica gel heater is still to be further improved.

For example, patent application publication No. CN111447697A discloses a method for manufacturing a silica gel heating sheet: the whole roll of the silica gel cloth is attached to the surface of the metal sheet to obtain the metal sheet attached with the silica gel cloth; putting the metal sheet attached with the silica gel cloth into a tunnel furnace for whole-roll hot vulcanization, so that the metal sheet and the silica gel are thermally cured into a whole to obtain an integrated metal sheet attached with the silica gel cloth; silk-screen printing a steel sheet on a whole roll of silica gel cloth, and drying the whole roll; carrying out corrosion processing on the whole steel sheet coil to obtain a corroded heating circuit semi-finished product; the whole roll of silica gel cloth is attached to the corroded semi-finished product of the heating circuit to obtain a semi-finished product of the silica gel heater; and cutting the semi-finished product of the silica gel heater by a laser machine to obtain a pad hole, plating tin on the pad hole, and welding a wire rod on the pad hole to obtain the whole-roll silica gel heater. The method optimizes the production process of the silica gel heater, improves the production efficiency of the silica gel heater and reduces the production cost, and the prepared silica gel heater is uniformly heated, but the silica gel heater obtained by the method has limited tensile strength, and is easy to cause the separation of the adhesive layer due to frequent tearing of external force when being used for a long time, so that the poor heat conduction and insulation are caused.

The problem of insufficient tensile strength can be solved by compounding and attaching the glass fiber cloth and the silica gel layer, the glass fiber cloth is an inorganic non-metallic material with excellent performance, has various varieties, has the advantages of good insulativity, strong heat resistance, good corrosion resistance and high mechanical strength, and can be used as a reinforcing material, an electrical insulating material and a heat insulation material in a composite material and can be complementarily reinforced with the flexibility of the silica gel. The bonding between the glass fiber cloth and the silica gel layer usually adopts pure fluorocarbon adhesives, because fluorocarbon has the characteristic of high temperature resistance, the adhesive is suitable for the long-time high-temperature heating of a silica gel heater, but the adhesives have two defects which are difficult to avoid: firstly, the cost of the fluorocarbon raw material is high, which is not beneficial to large-scale popularization and application; secondly, the fluorocarbon has low surface tension and poor compatibility with the silica gel layer, so that the adhesive force between the glass fiber cloth and the silica gel layer is insufficient, and the problem of heating efficiency reduction caused by the fact that the silica gel layer is peeled off or even falls off cannot be completely avoided even when the silica gel heater is used for a long time, particularly at a high temperature.

Disclosure of Invention

In order to solve the problems in the prior art, the invention provides the composite material for manufacturing the hot vulcanized silicone heater, which has the advantages of low cost, high temperature resistance, strong interlayer adhesion and higher tension, and the preparation method thereof.

The technical scheme of the invention is as follows:

the composite material for manufacturing the heat vulcanized silica gel heater sequentially comprises a first silicon sulfide adhesive layer, a nickel-chromium alloy layer, a second silicon sulfide adhesive layer and a glass fiber cloth layer from top to bottom, wherein the second silicon sulfide adhesive layer and the glass fiber cloth layer are bonded through an adhesive in a hot pressing mode. The composite material for manufacturing the hot vulcanized silica gel heater has a multilayer composite structure, and can remarkably improve the tensile strength on the premise of keeping the flexibility, thereby improving the stability and durability of the product.

As a further scheme of the invention, the adhesive comprises the following components in parts by weight: 60-90 parts of epoxy resin, 20-35 parts of polyester modified phenyl organosilicon, 5-10 parts of perfluoropolyether diol, 15-25 parts of epoxy diluent, 10-20 parts of epoxy curing agent, 5-10 parts of filler, 4-8 parts of melamine cyanurate and 0.5-2 parts of silane coupling agent.

In a further embodiment of the present invention, the epoxy resin in the adhesive of the present invention is selected from one or more of aromatic epoxy resin, novolac epoxy resin, and alicyclic epoxy resin, in order to achieve heat resistance, adhesion, and mechanical strength. Specifically, the epoxy resin is selected from one or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin and o-cresol formaldehyde epoxy resin. From the viewpoint of improving the insulation and corrosion resistance of the silica gel heater, bisphenol a type epoxy resin is preferably used; from the viewpoint of convenience in construction, bisphenol F epoxy resin is more preferably used because bisphenol F epoxy resin has a lower viscosity, has better impregnation performance for the glass fiber cloth, can sufficiently wet and wet the glass fiber cloth, and enhances the adhesion to the adjacent silica gel layer; in view of weather resistance, o-cresol novolac epoxy resins are preferably used because cured products of the o-cresol novolac epoxy resins have high crosslinking density and excellent thermal stability, water resistance and corrosion resistance; in addition, from the viewpoint of mechanical strength, the alicyclic epoxy resin is more preferably used because it has high compressive and tensile strength and maintains good mechanical and electrical properties even when exposed to high temperatures for a long period of time.

The epoxy resin of the present invention can be selected from common commercial products, such as CYD-128 resin of ba tomb petrochemical, DER331 resin of Dow chemical, 828XA resin of Shell company, NPEL128 resin of south Asia New Material Co., Ltd, 850S resin of Di Egyo, YD128 resin formed by Dongdu, NPPN631 resin of south Asia New Material Co., Ltd, CYDCN-208H resin of ba tomb petrochemical of China petrochemical group, SQCN704 resin of Shandong Shengquan New Material Co., Ltd, and the like.

The perfluoropolyether diol in the adhesive used in the invention can obviously improve the compatibility of the components, reduce the phase separation phenomenon of the adhesive in the preparation and curing processes and further improve the interlayer adhesion. As a further scheme of the invention, the main chain polyether structure of the perfluoropolyether diol in the adhesive is selected from one or more of perfluoropolyoxyethylene ether, perfluoropolyoxypropylene ether and polytetrafluoro furan ether glycol.

The perfluoropolyether diol of the invention can be selected from common commercial products, such as FOMBLIN D2 and E10H from Solvey company.

In a further embodiment of the present invention, the epoxy diluent in the present invention may be selected from common commercially available products, and specifically may be selected from one or more of a glycidyl ether type epoxy diluent, a glycidyl ester type epoxy diluent, and an alicyclic epoxy diluent, and the present invention is illustrated by taking the 501 diluent as an example, but not limited thereto. The 501 diluent manufacturers known in the art are Anhui Hengyuan, south Asia New materials, Inc., and the like.

In a further embodiment of the present invention, the epoxy curing agent in the present invention may be selected from common commercial products, and may be selected from one or more of polyamide epoxy curing agents and phenol aldehyde amine epoxy curing agents, for example, T31A of sambucus group.

As a further embodiment of the present invention, the filler in the present invention is preferably a heat conductive filler, specifically selected from one or more of silica, calcium carbonate, alumina, silicon nitride, aluminum nitride and silicon carbide. The heat-conducting filler can improve the interface compatibility of the adhesive and can improve the mechanical property and the heat-conducting dielectric property of the glass fiber cloth adhesive.

As a further scheme of the invention, the silane coupling agent in the invention can be selected from one or more of aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-aminopropylmethyldiethoxysilane and methyltrimethoxysilane. The silane coupling agent can combine the heat-conducting filler in a covalent bond mode, and is beneficial to the dispersion and fixation of the heat-conducting filler, so that the glass fiber and the adhesive are fully bonded, and delamination is not easy to occur. The silane coupling agent may be selected from common commercially available products, such as corning, Nanjing eosino chemical group, Xinyue group, and the like.

As a further scheme of the invention, the polyester modified phenyl organosilicon has the following structure:

wherein a represents an integer of 0 to 50, b represents an integer of 10 to 50, and c represents an integer of 0 to 10;

R¹to representWherein, represents the grafting site of the group, and m represents an integer of 4 to 15.

The polyester modified phenyl organosilicon provided by the invention has excellent high temperature resistance (generally can resist the high temperature of more than 300 ℃), has obvious insulativity, improves the hydrophobic and oleophobic properties of the conventional phenyl organosilicon, has good compatibility with other resins, and enhances the adhesive force with glass fiber cloth.

Further, in the polyester-modified phenyl silicone of the present invention, if the value b is less than 10, the heat resistance of the polyester-modified phenyl silicone is affected, and if the value b is more than 50, the polyester-modified phenyl silicone is poor in compatibility with other resins due to polarity, and therefore, the value b needs to be controlled within a proper range. Also, the c value corresponds to a segment as a part of side chain modification, which affects the silicon content of the whole molecule, and the higher the c value is, the better the compatibility of the resin is, but an excessively high c value has a negative influence on the heat resistance. In addition, m value has a relatively significant influence on the compatibility of the resin.

As a further scheme of the invention, the preparation method of the polyester modified phenyl organosilicon is as follows:

(1) under the conditions of nitrogen environment, platinum catalysis and 60-120 ℃ of reaction temperature, phenyl hydrogen-containing silicone oil and ethylene glycol monoallyl ether are subjected to hydrosilylation reaction to generate an organosilane alcohol intermediate, and then the excessive ethylene glycol monoallyl ether is removed under the vacuum condition of less than-0.095 MPa;

(2) under the conditions of nitrogen environment and reaction temperature of 80-130 ℃, the organosilicon alkyl alcohol intermediate and a certain amount of caprolactone are subjected to ring-opening esterification reaction under the action of an organic metal catalyst until the residue of the caprolactone is less than 0.5 percent.

As a further aspect of the present invention, the phenyl hydrogen silicone oil in step (1) may be obtained by directly purchasing products with corresponding specifications (phenyl content, hydrogen content and viscosity) from the market, such as company of corning. It is well known to those skilled in the art that the homemade process is generally a telomerization equilibrium reaction of silane monomers in the presence of an acidic catalyst. For example, the phenyl hydrogen-containing silicone oil is synthesized by mixing certain weight proportion of hydrogen-terminated silicone oil, octamethylcyclotetrasiloxane, tetramethyltetraphenylcyclotetrasiloxane and tetramethyltetrahydrocyclotetrasiloxane, and then under the catalysis of acidity of sulfuric acid, acid clay, other solid acid and the like at the reaction temperature of 30-60 ℃.

In a further embodiment of the present invention, the platinum catalyst is selected from one or more of platinum, chloroplatinic acid, tris (di-n-butyl sulfide) -trichlororhodium (III), bis (diethyl sulfide) -dichloroplatinum (II), and platinum-vinylsiloxane chelate.

As a further aspect of the present invention, the ethylene glycol monoallyl ether of the present invention can be commercially purchased from commercially available products, such as Hubei New materials, Inc., and Zhou Dang Xin chemical, Inc.

As a further scheme of the invention, the residue of caprolactone in the reaction system can be calibrated in the step (2) by an HPLC external standard method, and caprolactone of less than 0.5 wt% is controlled to be used as a reaction endpoint judgment standard.

As a further scheme of the invention, the organic metal catalyst in the step (2) is n-butyl zirconium, and the addition amount of the organic metal catalyst is 1.0-3.0% of the total mass of the reaction raw materials.

As a further scheme of the invention, the preparation method of the composite material for manufacturing the hot vulcanized silica gel heater comprises the following steps:

step (A): weighing epoxy resin, polyhydroxy crosslinking agent, epoxy diluent, filler, melamine cyanurate and silane coupling agent according to a certain proportion, adding the above-mentioned materials into a stirring machine to make high-speed dispersion and stirring, after uniformly dispersed adding epoxy curing agent, continuously stirring so as to obtain adhesive;

step (B): brushing the adhesive prepared in the step (A) on one side of the glass fiber cloth, then sequentially rolling the unvulcanized second silica gel layer, the nichrome heating component and the unvulcanized first silica gel layer by layer to one side of the glass fiber cloth coated with the adhesive, and then putting the glass fiber cloth layer, the second silica gel layer, the nichrome layer and the first silicon sulfide gel layer into a tunnel furnace for high-temperature vulcanization to form a composite structure of the glass fiber cloth layer, the second silica gel layer, the nichrome layer and the first silicon sulfide gel.

As a further scheme of the invention, the surface temperature of a roller of the calender is controlled to be 5-15 ℃ in the calendering process, and the calendering is carried out at the speed of 3-5 m/min; the temperature of the high-temperature vulcanization is 110-170 ℃.

Has the advantages that:

according to the invention, the adhesive force of the adhesive between the silica gel layer and the glass fiber cloth layer is improved by preparing the polyester modified phenyl organosilicon, and meanwhile, the heat resistance of the adhesive is greatly improved, so that the hidden danger of delamination and peeling of a common silica gel heater after long-time high-temperature use is avoided.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in further detail below. In the following examples, those whose operations are not subject to the conditions indicated, are carried out according to the conventional conditions or conditions recommended by the manufacturer.

Example 1

A composite material for manufacturing a hot vulcanized silica gel heater is prepared by the following steps:

step (A): weighing 70 parts of CYD-128 resin (epoxy ester is 0.52mol/100g) of the ba ling petrochemical industry, 23 parts of polyester modified phenyl organosilicon, 5 parts of FOMBLIN D2 of Solvey company, 22 parts of 501 epoxy diluent, 7 parts of silicon dioxide, 6 parts of melamine cyanurate and 1 part of 3-glycidyl ether oxypropyltrimethoxysilane, adding the mixture into a stirrer to perform high-speed dispersion stirring, adding 15 parts of T31A epoxy curing agent of a trilobate group after uniform dispersion, and continuing stirring to prepare an adhesive for later use;

step (B): brushing the adhesive prepared in the step (A) on one side of the glass fiber cloth, then sequentially rolling the unvulcanized second silica gel layer, the nichrome heating component and the unvulcanized first silica gel layer to one side of the glass fiber cloth coated with the adhesive, and then putting the glass fiber cloth into a tunnel furnace for high-temperature vulcanization to form a composite structure of the glass fiber cloth layer, the second silica gel layer, the nichrome layer and the first silicon sulfide rubber layer. The process conditions of the calendering are as follows: cooling and circulating the calender roller, controlling the surface temperature of the calender roller to be 10 ℃, and calendering at the speed of 3 m/min; the process conditions of the high-temperature vulcanization are as follows: the temperature of the drying tunnel in the tunnel furnace is controlled to be 120 ℃. And then cooled to room temperature to obtain the composite material for manufacturing the hot vulcanized silica gel heater.

The preparation method of the polyester modified phenyl organosilicon comprises the following steps:

introducing nitrogen into a reaction kettle equipped with a mechanical stirrer, a condenser pipe, a thermometer and a kettle bottom vent hole, and then respectively adding 17 parts of ethylene glycol monoallyl ether and 100 parts of HMe with the average formula₂SiO(SiMe₂O)₅(PhSiMeO)₁₆(HSiMeO)₂SiMe₂H phenyl hydrogen polysiloxane (hydrogen content 0.14%), when heating to 60 deg.C, adding 0.12 part of isopropanol solution of platinum-vinyl siloxane chelate with mass fraction of 2% in two batches, heating to 70 deg.C, stirring to react for 3 hours, and removing excessive ethylene glycol monoallyl ether under vacuum of less than-0.095 MPa to obtain light yellow oily substance which is an organic silanol intermediate;

then maintaining a nitrogen environment, adding 101 parts of caprolactone and n-butyl zirconium accounting for 2 wt% of the total mass of the raw materials into the organic silane-based alcohol intermediate, carrying out heat preservation reaction at 90 ℃, monitoring the caprolactone residue in the system by adopting an HPLC external standard method, finishing the reaction when the caprolactone content is less than 0.5 wt% to obtain light yellow polyester modified phenyl organosilicon,¹H-NMR confirmed the structure as follows:

wherein the content of the first and second substances,

example 2

A composite material for manufacturing a hot vulcanized silica gel heater is prepared by the following steps:

step (A): weighing 84 parts of CYD-128 resin (epoxy ester is 0.52mol/100g) of the ba ling petrochemical industry, 20 parts of polyester modified phenyl organosilicon, 8 parts of FOMBLIN D2 of Solvey company, 17 parts of 501 epoxy diluent, 9 parts of silicon dioxide, 4 parts of melamine cyanurate and 0.5 part of aminopropyltriethoxysilane, adding into a stirrer for high-speed dispersion stirring, adding 12 parts of T31A epoxy curing agent of a Sanmu group after uniform dispersion, and continuously stirring to prepare an adhesive for later use;

step (B): brushing the adhesive prepared in the step (A) on one side of the glass fiber cloth, then sequentially rolling the unvulcanized second silica gel layer, the nichrome heating component and the unvulcanized first silica gel layer to one side of the glass fiber cloth coated with the adhesive, and then putting the glass fiber cloth into a tunnel furnace for high-temperature vulcanization to form a composite structure of the glass fiber cloth layer, the second silica gel layer, the nichrome layer and the first silicon sulfide rubber layer. The process conditions of the calendering are as follows: cooling and circulating the calender roller, controlling the surface temperature of the calender roller to be 8 ℃, and calendering at the speed of 3 m/min; the process conditions of the high-temperature vulcanization are as follows: the temperature of the drying tunnel in the tunnel furnace is controlled to be 110 ℃. And then cooled to room temperature to obtain the composite material for manufacturing the hot vulcanized silica gel heater.

The preparation method of the polyester modified phenyl organosilicon comprises the following steps:

introducing nitrogen into a reaction kettle equipped with a mechanical stirrer, a condenser pipe, a thermometer and a kettle bottom vent hole, and then respectively adding 21.8 parts of ethylene glycol monoallyl ether and 100 parts of HMe with the average formula₂SiO(PhSiMeO)₂₅(HSiMeO)₅SiMe₂H phenyl hydrogen polysiloxane (hydrogen content 0.177%), when heating to 60 deg.C, adding 0.12 part of isopropanol solution of platinum-vinyl siloxane chelate with mass fraction of 2% in two batches, heating to 85 deg.C, stirring to react for 3 hr, and removing excessive ethylene glycol monoallyl ether under vacuum of less than-0.095 MPa to obtain yellowish oily substance as organic silanol intermediate;

then maintaining a nitrogen environment, adding 85 parts of caprolactone and n-butyl zirconium accounting for 1 wt% of the total mass of the raw materials into the organic silane-based alcohol intermediate, carrying out heat preservation reaction at 110 ℃, monitoring the caprolactone residue in the system by adopting an HPLC external standard method, finishing the reaction when the caprolactone content is less than 0.5 wt% to obtain light yellow polyester modified phenyl organosilicon,¹H-NMR confirmed the structure as follows:

wherein the content of the first and second substances,

example 3

A composite material for manufacturing a hot vulcanized silica gel heater is prepared by the following steps:

step (A): weighing 60 parts of NPPN631 resin of new south Asia material Co., Ltd, 30 parts of polyester modified phenyl organosilicon, 5 parts of FOMBLIN D2 of Solvey Co., 20 parts of 501 epoxy diluent, 10 parts of calcium carbonate, 7 parts of melamine cyanurate and 2 parts of gamma-methacryloxypropyl trimethoxysilane, adding into a stirrer for high-speed dispersion and stirring, adding 10 parts of T31A epoxy curing agent of a tribasic group after uniform dispersion, and continuing stirring to prepare an adhesive for later use;

step (B): brushing the adhesive prepared in the step (A) on one side of the glass fiber cloth, then sequentially rolling the unvulcanized second silica gel layer, the nichrome heating component and the unvulcanized first silica gel layer to one side of the glass fiber cloth coated with the adhesive, and then putting the glass fiber cloth into a tunnel furnace for high-temperature vulcanization to form a composite structure of the glass fiber cloth layer, the second silica gel layer, the nichrome layer and the first silicon sulfide rubber layer. The process conditions of the calendering are as follows: cooling and circulating the calender roller, controlling the surface temperature of the calender roller to be 5 ℃, and calendering at the speed of 3 m/min; the process conditions of the high-temperature vulcanization are as follows: the temperature of the drying tunnel in the tunnel furnace is controlled to be 150 ℃. And then cooled to room temperature to obtain the composite material for manufacturing the hot vulcanized silica gel heater.

The preparation method of the polyester modified phenyl organosilicon comprises the following steps:

introducing nitrogen into a reaction kettle equipped with a mechanical stirrer, a condenser pipe, a thermometer and a kettle bottom vent hole, and then respectively adding 13.5 parts of ethylene glycol monoallyl ether and 100 parts of HMe with the average formula₂SiO(SiMe₂O)₁₅(PhSiMeO)₃₅(HSiMeO)₅SiMe₂H phenyl hydrogen polysiloxane (hydrogen content 0.109%), heating to 60 deg.C, adding 0.12 parts of isopropanol solution of platinum-vinyl siloxane chelate with the mass fraction of 2%, heating to 95 ℃, stirring for reaction for 3 hours, and removing excessive ethylene glycol monoallyl ether under the vacuum of less than-0.095 MPa to obtain a light yellow oily substance which is an organic silane alcohol intermediate;

then maintaining nitrogen environment, adding 101.5 parts of caprolactone and n-butyl zirconium accounting for 2 wt% of the total mass of the raw materials into the organic silane-based alcohol intermediate, carrying out heat preservation reaction at 120 ℃, monitoring the caprolactone residue in the system by adopting an HPLC external standard method, finishing the reaction when the caprolactone content is less than 0.5 wt% to obtain light yellow polyester modified phenyl organosilicon,¹H-NMR confirmed the structure as follows:

wherein the content of the first and second substances,

example 4

A composite material for manufacturing a hot vulcanized silica gel heater is prepared by the following steps:

step (A): weighing 90 parts of CYDCN-208H resin of the Baling petrochemical group of China petrochemical, 35 parts of polyester modified phenyl organosilicon, 10 parts of E10H of Solvey company, 20 parts of 501 epoxy diluent, 5 parts of alumina, 8 parts of melamine cyanurate and 1 part of gamma-aminopropyl methyl diethoxy silane, adding into a stirrer to perform high-speed dispersion stirring, adding 20 parts of T31A type epoxy curing agent of the Sanmu group after uniform dispersion, and continuing stirring to prepare an adhesive for later use;

step (B): brushing the adhesive prepared in the step (A) on one side of the glass fiber cloth, then sequentially rolling the unvulcanized second silica gel layer, the nichrome heating component and the unvulcanized first silica gel layer to one side of the glass fiber cloth coated with the adhesive, and then putting the glass fiber cloth into a tunnel furnace for high-temperature vulcanization to form a composite structure of the glass fiber cloth layer, the second silica gel layer, the nichrome layer and the first silicon sulfide rubber layer. The process conditions of the calendering are as follows: cooling and circulating the calender roller, controlling the surface temperature of the calender roller to be 10 ℃, and calendering at the speed of 3 m/min; the process conditions of the high-temperature vulcanization are as follows: the temperature of the drying tunnel in the tunnel furnace is controlled to be 150 ℃. And then cooled to room temperature to obtain the composite material for manufacturing the hot vulcanized silica gel heater.

The preparation method of the polyester modified phenyl organosilicon comprises the following steps:

introducing nitrogen into a reaction kettle equipped with a mechanical stirrer, a condenser pipe, a thermometer and a kettle bottom vent hole, and then respectively adding 25.6 parts of ethylene glycol monoallyl ether and 100 parts of HMe with the average formula₂SiO(SiMe₂O)₁₀(PhSiMeO)₃₀(HSiMeO)₁₀SiMe₂H phenyl hydrogen polysiloxane (hydrogen content 0.209%), heating to 50 deg.C, adding 0.14 part of isopropanol solution of platinum-vinyl siloxane chelate with mass fraction of 2% in two batches, heating to 110 deg.C, stirring for reaction for 3 hr, and removing excessive ethylene glycol monoallyl ether under vacuum of less than-0.095 Mpa to obtain light yellow oily substance as organic silanol intermediate;

then maintaining nitrogen environment, adding 200.5 parts of caprolactone and n-butyl zirconium accounting for 2 wt% of the total mass of the raw materials into the organic silane-based alcohol intermediate, carrying out heat preservation reaction at 130 ℃, monitoring the caprolactone residue in the system by adopting an HPLC external standard method, finishing the reaction when the caprolactone content is less than 0.5 wt% to obtain light yellow polyester modified phenyl organosilicon,¹H-NMR confirmed the structure as follows:

wherein the content of the first and second substances,

example 5

A composite material for manufacturing a hot vulcanized silica gel heater is prepared by the following steps:

step (A): weighing SQCN704 resin of Shandong Shengquan New Material Co., Ltd, 30 parts of polyester modified phenyl organosilicon, 8 parts of FOMBLIN D2 of Solvey Co., 25 parts of 501 epoxy diluent, 10 parts of silicon nitride, 6 parts of melamine cyanurate and 2 parts of methyltrimethoxysilane, adding into a stirrer for high-speed dispersion and stirring, adding 15 parts of T31A type epoxy curing agent of Sanmu group after uniform dispersion, and continuously stirring to prepare an adhesive for later use;

step (B): brushing the adhesive prepared in the step (A) on one side of the glass fiber cloth, then sequentially rolling the unvulcanized second silica gel layer, the nichrome heating component and the unvulcanized first silica gel layer to one side of the glass fiber cloth coated with the adhesive, and then putting the glass fiber cloth into a tunnel furnace for high-temperature vulcanization to form a composite structure of the glass fiber cloth layer, the second silica gel layer, the nichrome layer and the first silicon sulfide rubber layer. The process conditions of the calendering are as follows: cooling and circulating the calender roller, controlling the surface temperature of the calender roller to be 10 ℃, and calendering at the speed of 3 m/min; the process conditions of the high-temperature vulcanization are as follows: the temperature of the drying tunnel in the tunnel furnace is controlled to be 140 ℃. And then cooled to room temperature to obtain the composite material for manufacturing the hot vulcanized silica gel heater.

The preparation method of the polyester modified phenyl organosilicon comprises the following steps:

introducing nitrogen into a reaction kettle equipped with a mechanical stirrer, a condenser pipe, a thermometer and a kettle bottom vent hole, and then respectively adding 14 parts of ethylene glycol monoallyl ether and 100 parts of HMe with the average formula₂SiO(SiMe₂O)₂₀(PhSiMeO)₃₀(HSiMeO)₅SiMe₂H phenyl hydrogen polysiloxane (hydrogen content 0.115%), when heating to 55 deg.C, adding 0.14 part of isopropanol solution of platinum-vinyl siloxane chelate with mass fraction of 2% in two batches, heating to 100 deg.C, stirring to react for 3 hours, then removing excessive ethylene glycol monoallyl ether under vacuum of less than-0.095 Mpa to obtain light yellow oily substance which is organic silanol intermediate;

then keeping nitrogen environment, adding 137.5 parts of caprolactone and n-butyl zirconium accounting for 2 wt% of the total mass of the raw materials into the organosilane alcohol intermediate, keeping the temperature at 120 ℃ for reaction,monitoring the caprolactone residue in the system by HPLC external standard method, ending the reaction when the caprolactone content is less than 0.5 wt% to obtain light yellow polyester modified phenyl organosilicon,¹H-NMR confirmed the structure as follows:

wherein the content of the first and second substances,

example 6

A composite material for manufacturing a hot vulcanized silica gel heater is prepared by the following steps:

step (A): weighing 85 parts of CYD-128 resin (epoxy ester is 0.52mol/100g) of the ba ling petrochemical industry, 35 parts of polyester modified phenyl organosilicon, 5 parts of E10H of Solvey company, 20 parts of 501 epoxy diluent, 8 parts of aluminum nitride, 6 parts of melamine cyanurate and 1 part of methyltrimethoxysilane, adding into a stirrer for high-speed dispersion and stirring, adding 15 parts of T31A epoxy curing agent of a Sanmu group after uniform dispersion, and continuing stirring to prepare an adhesive for later use;

step (B): brushing the adhesive prepared in the step (A) on one side of the glass fiber cloth, then sequentially rolling the unvulcanized second silica gel layer, the nichrome heating component and the unvulcanized first silica gel layer to one side of the glass fiber cloth coated with the adhesive, and then putting the glass fiber cloth into a tunnel furnace for high-temperature vulcanization to form a composite structure of the glass fiber cloth layer, the second silica gel layer, the nichrome layer and the first silicon sulfide rubber layer. The process conditions of the calendering are as follows: cooling and circulating the calender roller, controlling the surface temperature of the calender roller to be 15 ℃, and calendering at the speed of 3 m/min; the process conditions of the high-temperature vulcanization are as follows: the temperature of the drying tunnel in the tunnel furnace is controlled to be 170 ℃. And then cooled to room temperature to obtain the composite material for manufacturing the hot vulcanized silica gel heater.

The preparation method of the polyester modified phenyl organosilicon comprises the following steps:

to one mounting machineIntroducing nitrogen into a reaction kettle with a mechanical stirring device, a condenser pipe, a thermometer and a kettle bottom vent hole, and then respectively adding 10.6 parts of ethylene glycol monoallyl ether and 100 parts of HMe with the average general formula₂SiO(SiMe₂O)₁₀(PhSiMeO)₅₀(HSiMeO)₅SiMe₂H phenyl hydrogen polysiloxane (hydrogen content 0.086%), heating to 60 deg.C, adding 0.14 part of isopropanol solution of platinum-vinyl siloxane chelate with mass fraction of 2% in two batches, heating to 120 deg.C, stirring to react for 4 hr, and removing excessive ethylene glycol monoallyl ether under vacuum of less than-0.095 MPa to obtain light yellow oily substance as organic silanol intermediate;

then maintaining nitrogen environment, adding 155.2 parts of caprolactone and n-butyl zirconium accounting for 3 wt% of the total mass of the raw materials into the organic silane-based alcohol intermediate, carrying out heat preservation reaction at 130 ℃, monitoring the caprolactone residue in the system by adopting an HPLC external standard method, finishing the reaction when the caprolactone content is less than 0.5 wt% to obtain light yellow polyester modified phenyl organosilicon,¹H-NMR confirmed the structure as follows:

wherein the content of the first and second substances,

the above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

And (3) performance testing:

the following tests were performed on samples prepared in examples 1-6 and on commercially available silica gel heating materials prepared from pure fluorocarbon adhesives, and the results are shown in Table 1 below:

adhesion force: testing the 90-degree peeling force (the sample width is 2.5cm, and the peeling speed is 10mm/min) between the glass fiber cloth layer and the silica sulfide layer by adopting a CMT8202 type electronic universal testing machine;

flame retardancy: the samples were tested according to GB/T2408-;

instantaneous high temperature resistance: baking in a muffle furnace at 400 ℃/10s to observe the yellowing of the appearance;

thermal conductivity: testing was performed according to ASTM D5470.

TABLE 1

The data show that the composite material for manufacturing the heat-vulcanized silica gel heater has excellent high-temperature resistance, and in addition, the adhesive force of the combination between the glass fiber layer and the vulcanized silica gel layer is obviously improved, the flame retardant effect is good, the heat conduction effect is outstanding, the cost is low, and the application prospect is good.