WO2018036426A1 - 防火玻璃用改性纳米复合聚硫密封胶及其制备 - Google Patents

防火玻璃用改性纳米复合聚硫密封胶及其制备 Download PDF

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WO2018036426A1
WO2018036426A1 PCT/CN2017/098067 CN2017098067W WO2018036426A1 WO 2018036426 A1 WO2018036426 A1 WO 2018036426A1 CN 2017098067 W CN2017098067 W CN 2017098067W WO 2018036426 A1 WO2018036426 A1 WO 2018036426A1
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parts
modified
graphene
fireproof glass
weight
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French (fr)
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段曦东
李晓丰
毛志浩
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广东纳路纳米科技有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • 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
    • C09J181/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Adhesives based on polysulfones; Adhesives based on derivatives of such polymers
    • C09J181/04—Polysulfides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Definitions

  • the invention relates to the technical field of sealant, in particular to a modified nano-composite polysulfide sealant for fireproof glass and preparation thereof.
  • the polysulfide sealant formed by vulcanization is usually a kind of sealing material prepared by mechanically stirring and mixing a liquid polysulfide rubber as a matrix and adding an appropriate amount of filler, auxiliary agent and vulcanizing agent.
  • the polysulfide sealant is reduced in weather resistance due to the long-term effects of environmental humidity, oxygen, ozone, ultraviolet rays and other factors. The sealant gradually loses its elasticity and the adhesion between the fireproof glass and the fireproof glass.
  • the present invention adopts the following technical solutions:
  • the modified nanocomposite polysulfide sealant for fireproof glass of the invention comprises: a base rubber component and a vulcanized component in a weight ratio of 100:5-20;
  • the base rubber component comprises the following parts by weight: 60-100 parts of liquid polysulfide rubber, 0.01-5 parts of modified nano-powder, 10-50 parts of reinforcing filler, 0.1-5 parts of silane coupling agent;
  • the vulcanized component comprises the following parts by weight: 5 to 20 parts of a tackifier, 5 to 30 parts of a vulcanizing agent, and 0.1 to 5 parts of a vulcanization accelerator;
  • the liquid polysulfide rubber has a number average molecular weight of 1000 to 4000;
  • the modified nano powder is one of modified white graphene, modified graphene, and graphene oxide.
  • the weight ratio of the base rubber component to the vulcanized component is 100:10;
  • the base rubber component comprises the following parts by weight: 65-85 parts of liquid polysulfide rubber, 0.01-3 parts modified Nano powder, 15 to 40 parts of reinforcing filler, 0.2 to 3 parts of silane coupling agent;
  • the vulcanized component comprises the following parts by weight: 5 to 15 parts of a tackifier, 6 to 20 parts of a vulcanizing agent, and 0.1 to 3.5 parts of a vulcanization accelerator.
  • the liquid polysulfide rubber is a matrix of polysulfide sealant, and the number average molecular weight directly determines the mechanical properties of the polysulfide sealant after vulcanization. Further preferably, the liquid polysulfide rubber has a number average molecular weight of 3,000, which has more Excellent plasticity and good mechanical properties.
  • the modified white graphene is treated by 1 to 10 layers of white graphene via a long-chain Lewis base, a long-chain Lewis acid, a sulfonate, a quaternary amine or a nonionic surfactant, thereby increasing white stone.
  • a surfactant such as polyvinylpyrrolidone (PVP) or sodium dodecylbenzenesulfonate (SDBS) to increase the graphene Affinity to the substrate.
  • the long-chain Lewis base is oleylamine or the like; the long-chain Lewis acid is long-chain borane or the like; the sulfonate is sodium dodecylbenzenesulfonate or the like; and the quaternary amine is Cetylpyridinium bromide or the like; the nonionic surfactant is a polyethylene oxide alkyl alcohol amide or the like.
  • the reinforcing filler is one of nano silica, nano calcium carbonate, and carbon black;
  • the silane coupling agent is one of KH-550, KH-560, and KH-570;
  • the tackifier includes one of an acrylic resin, an epoxy resin, and glycidyl methacrylate;
  • the vulcanizing agent includes one of calcium peroxide, zinc peroxide, and manganese dioxide;
  • the accelerator is diphenyl hydrazine, which can accelerate the room temperature vulcanization process of the liquid polysulfide rubber.
  • the vulcanizing agent is manganese dioxide, which is an optimum vulcanizing agent for room temperature vulcanization of polysulfide rubber.
  • the preparation method of the modified nano-composite polysulfide sealant for fireproof glass of the invention comprises:
  • Step 1) Select one of modified white graphene, modified graphene, and graphene oxide as the nano powder;
  • the modification method is: 1-10 layers of white graphene with a mass percentage of 0.1% Chain Lewis base, long-chain Lewis acid, sulfonate, quaternary amine or non-ionic aqueous solution for 24 hours, after centrifugation, vacuum drying to obtain modified white graphene powder; 1 to 10 layers of graphene dispersed in concentration After being ultrasonicated in an aqueous solution of 0.1 mg/ml polyvinylpyrrolidone or sodium dodecylbenzenesulfonate for 12 hours, the modified graphene powder is obtained by centrifugation and vacuum drying;
  • Step 2) Preparation of the base rubber component: the liquid polysulfide rubber and the silane coupling agent are respectively weighed and mixed according to the parts by weight, and then the nano-modified powder and the reinforcing filler are sequentially added, and the components are in the range of 35 to 100. Mixing at °C for 10-60min, grinding several times until a uniform base rubber component is obtained;
  • Step 3 Preparation of the vulcanized component: a certain amount of the tackifier, the vulcanizing agent and the vulcanization accelerator are weighed according to the parts by weight, and the components are mixed and stirred to obtain a vulcanized component;
  • Step 4) The base rubber component prepared in the step 2) and the vulcanized component prepared in the step 3) are uniformly mixed by weight ratio to obtain a modified nano-composite polysulfide sealant for fireproof glass, and uniformly coated on the edge of the fireproof glass.
  • the desired sealing effect can be achieved in all four weeks.
  • the base rubber component mixing temperature in the step 2) is 60 °C.
  • the modified nano-powder is selected from 1 to 10 layers of modified white graphene, modified graphene or graphene oxide.
  • the sheet layer is compact and uniform, and the number of barrier sheets is large.
  • the gas is bypassed in the polysulfide rubber. Lengthening, a small amount of addition can well block the passage of gas, increase the airtightness of the polysulfide rubber after curing; at the same time, the surfactant-treated white graphene, graphene and graphite oxide with more active groups on the surface
  • the olefin is added in a small amount, the wettability with the substrate can be achieved, and the reinforcing effect is enhanced, and the mechanical strength of the polysulfide rubber is improved.
  • the invention improves the airtightness and the mechanical strength reduction caused by the aging of environmental factors due to the aging of the polysulfide sealant for fireproof glass, effectively protects the stability of the fireproof liquid inside the fireproof glass, prevents the generation of bubbles in the fireproof liquid of the fireproof glass seal, and makes the fireproof The refractory and thermal insulation properties of the glass are protected.
  • the product of the invention prolongs the service life of the fireproof glass without affecting the appearance, has simple process, is easy to operate, and has high application value.
  • Step 1) modification of nano powder 1 to 10 layers of white graphene are selected, soaked in 0.1% aqueous oleylamine solution for 24 hours, and centrifuged and vacuum dried to obtain white graphene modified powder;
  • Step 2) Preparation of the base rubber component: 100 parts of the liquid polysulfide rubber and 1 part of the silane coupling agent are respectively weighed and added to the mixer, mixed and stirred for 5 minutes, and then 0.1 parts are sequentially added to prepare the step 1)
  • the modified white graphene powder and 30 parts of nano-silica are kneaded for 45 min, the mixing temperature is 40 ° C, and the components are uniformly mixed and stirred, and then repeatedly ground by three-roll mill for three times to obtain a base rubber component. .
  • Step 3 Preparation of the vulcanized component: 10 parts of epoxy resin, 5 parts of manganese dioxide and 1 part of diphenyl hydrazine are respectively weighed in parts by weight, added to a kneader, stirred at room temperature, and uniformly passed through a three-roll mill. The vulcanized component was obtained after repeated grinding three times.
  • Step 4) The base rubber component prepared in the step 2) and the vulcanized component prepared in the step 3) are uniformly mixed and stirred at a weight ratio of 100:6 to obtain a modified nano-composite polysulfide sealant for fireproof glass, which is uniform after completion. Coated around the edge of the fireproof glass.
  • Step 1) modification of the nano powder 1 to 10 layers of white graphene are selected by immersing in a 0.1% aqueous solution of oleylamine for 24 hours, and after centrifugation and vacuum drying, a white graphene-modified powder is obtained;
  • Step 2) Preparation of the base rubber component: 100 parts of the liquid polysulfide rubber and 5 parts of the silane coupling agent are respectively weighed and added to the kneader for 5 minutes, and then 1 part of the step 1) is prepared.
  • the modified white graphene powder and 10 parts of nano-silica are kneaded for 45 min, the mixing temperature is 80 ° C, and the components are mixed and stirred uniformly, and then repeatedly ground for three times by a three-roll mill to obtain a base rubber component. .
  • Step 3 Preparation of the vulcanized component: 20 parts of epoxy resin, 15 parts of manganese dioxide and 5 parts of diphenyl hydrazine are respectively weighed in parts by weight, added to a kneader, stirred at room temperature, and uniformly passed through a three-roll mill. The vulcanized component was obtained after repeated grinding three times.
  • Step 4) The base rubber component prepared in the step 2) and the vulcanized component prepared in the step 3) are uniformly mixed and stirred at a weight ratio of 100:15 to obtain a modified nano-composite polysulfide sealant for fireproof glass, which is uniform after completion. Coated around the edge of the fireproof glass.
  • Step 1) modification of the nano powder 1 to 10 layers of white graphene are selected by immersing in a 0.1% aqueous solution of oleylamine for 24 hours, and after centrifugation and vacuum drying, a white graphene-modified powder is obtained;
  • Step 2) Preparation of the base rubber component: 100 parts of the liquid polysulfide rubber and 1 part of the silane coupling agent are respectively weighed and added to the mixer, mixed and stirred for 5 minutes, and then 0.3 parts are sequentially added in step 1).
  • the prepared modified white graphene powder and 25 parts of nano-silica are kneaded for 45 min, the mixing temperature is 60 ° C, and the components are uniformly mixed and stirred, and then repeatedly ground by three-roll mill for three times to obtain a base rubber group. Share.
  • Step 3 Preparation of the vulcanized component: 15 parts of epoxy resin, 5 parts of manganese dioxide and 1 part of diphenyl hydrazine are respectively weighed and added to the mixer at room temperature, mixed and stirred uniformly, and passed through a three-roll mill. The vulcanized component was obtained after repeated grinding three times.
  • Step 4) The base rubber component prepared in the step 2) and the vulcanized component prepared in the step 3) are uniformly mixed and stirred at a weight ratio of 100:10 to obtain a modified nano-composite polysulfide sealant for fireproof glass, and uniformly coated after completion. Covered around the edge of the fireproof glass.
  • Step 1) Modification of the nano powder 1 to 10 layers of graphene are dispersed in a 0.1 mg/ml aqueous solution of polyvinylpyrrolidone for 12 hours, and centrifuged and vacuum-dried to obtain a graphene-modified powder.
  • Step 2) Preparation of the base rubber component: 100 parts of the liquid polysulfide rubber and 1 part of the silane coupling agent are respectively weighed and added to the mixer to be mixed and stirred for 5 minutes, and then 0.2 parts are sequentially added to prepare the step 1).
  • the modified graphene powder and 30 parts of nano-silica were kneaded for 45 min, and the kneading temperature was 40 ° C.
  • the base rubber component was obtained by repeated grinding three times through a three-roll mill.
  • Step 3 Preparation of the vulcanized component: 10 parts of epoxy resin, 5 parts of manganese dioxide and 1 part of diphenyl hydrazine are respectively weighed in parts by weight, added to a kneader, stirred at room temperature, and uniformly passed through a three-roll mill. The vulcanized component was obtained after repeated grinding three times.
  • Step 4) The base rubber component prepared in the step 2) and the vulcanized component prepared in the step 3) are uniformly mixed and stirred at a weight ratio of 100:6 to obtain a modified nano-composite polysulfide sealant for fireproof glass, which is uniform after completion. Coated around the edge of the fireproof glass.
  • Step 1) 1 to 10 layers of graphene are dispersed in a 0.1 mg/ml aqueous solution of polyvinylpyrrolidone for 12 hours, and centrifuged and vacuum-dried to obtain a graphene-modified powder.
  • Step 2) Preparation of the base rubber component: 100 parts of the liquid polysulfide rubber and 5 parts of the silane coupling agent are respectively weighed and added to the kneader for 5 minutes, and then 1 part of the step 1) is prepared. The modified graphene powder and 10 parts of nano-silica were kneaded for 45 min, and the kneading temperature was 80 ° C. After mixing and stirring the components, the base rubber component was obtained by repeated grinding three times through a three-roll mill.
  • Step 3 Preparation of the vulcanized component: 20 parts of epoxy resin, 15 parts of manganese dioxide and 5 parts of diphenyl hydrazine are respectively weighed in parts by weight, added to a kneader, stirred at room temperature, and uniformly passed through a three-roll mill. The vulcanized component was obtained after repeated grinding three times.
  • Step 4) The base rubber component prepared in the step 2) and the vulcanized component prepared in the step 3) are uniformly mixed and stirred at a weight ratio of 100:15 to obtain a modified nano-composite polysulfide sealant for fireproof glass, which is uniform after completion. Coated around the edge of the fireproof glass.
  • Step 1) Modification of the nano powder 1 to 10 layers of graphene are dispersed in a 0.1 mg/ml aqueous solution of polyvinylpyrrolidone for 12 hours, and centrifuged and vacuum-dried to obtain a graphene-modified powder.
  • Step 2) Preparation of the base rubber component: 100 parts of the liquid polysulfide rubber and 1 part of the silane coupling agent are respectively weighed and added to the mixer, mixed and stirred for 5 minutes, and then 0.5 parts are sequentially added to prepare the step 1)
  • the modified graphene powder and 25 parts of nano-silica were kneaded for 45 min, and the kneading temperature was 60 ° C.
  • the base rubber component was obtained by repeated grinding three times through a three-roll mill.
  • Step 3 Preparation of the vulcanized component: 15 parts of epoxy resin, 5 parts of manganese dioxide and 1 part of diphenyl hydrazine are respectively weighed and added to the mixer at room temperature, mixed and stirred uniformly, and passed through a three-roll mill. The vulcanized component was obtained after repeated grinding three times.
  • Step 4) The base rubber component prepared in the step 2) and the vulcanized component prepared in the step 3) are uniformly mixed and stirred at a weight ratio of 100:10 to obtain a modified nano-composite polysulfide sealant for fireproof glass, which is uniform after completion. Coated around the edge of the fireproof glass.
  • Step 1) Preparation of the base rubber component: 100 parts of liquid polysulfide rubber and 1 part of silane coupling agent are respectively weighed and added to the mixer for mixing for 5 minutes, and then 0.1 part of graphene oxide powder is sequentially added. The body and 30 parts of nano-silica were kneaded for 45 min, the kneading temperature was 40 ° C, and the components were mixed and stirred uniformly, and then repeatedly ground three times by a three-roll mill to obtain a base rubber component.
  • Step 2) Preparation of vulcanized component: 10 parts of epoxy resin, 5 parts of manganese dioxide and 1 part of diphenyl hydrazine are respectively weighed in parts by weight, added to a kneader, stirred at room temperature, and uniformly passed through a three-roll mill. The vulcanized component was obtained after repeated grinding three times.
  • Step 3) The base rubber component prepared in the step 2) and the vulcanized component prepared in the step 3) are uniformly mixed and stirred at a weight ratio of 100:6 to obtain a modified nano-composite polysulfide sealant for fireproof glass, which is uniform after completion. Coated around the edge of the fireproof glass.
  • Step 1) Preparation of the base rubber component: 100 parts of liquid polysulfide rubber and 5 parts of silane coupling agent are respectively weighed and added to the mixer for mixing for 5 minutes, and then 1 part of graphene oxide powder is sequentially added. The mixture was mixed with 10 parts of nano-silica for 45 minutes, and the mixing temperature was 80 ° C. After mixing and stirring the components, the base rubber component was obtained by repeated grinding three times through a three-roll mill.
  • Step 2) Preparation of the vulcanized component: 20 parts of epoxy resin, 15 parts of manganese dioxide and 5 parts of diphenyl hydrazine are respectively weighed in parts by weight, added to a kneader, stirred at room temperature, and uniformly passed through a three-roll mill. The vulcanized component was obtained after repeated grinding three times.
  • Step 3) The base rubber component prepared in the step 2) and the vulcanized component prepared in the step 3) are uniformly mixed and stirred at a weight ratio of 100:15 to obtain a modified nano-composite polysulfide sealant for fireproof glass, which is uniform after completion. Coated around the edge of the fireproof glass.
  • Step 1) Preparation of the base rubber component: 100 parts of liquid polysulfide rubber and 1 part of silane coupling agent are respectively weighed and added to the mixer to be mixed and stirred for 5 minutes, and then 0.4 parts of graphite oxide is sequentially added. The olefin powder and 25 parts of nano silica were kneaded for 45 min, and the kneading temperature was 60 ° C. After mixing and stirring the components, the base rubber component was obtained by repeatedly grinding three times through a three-roll mill.
  • Step 2) Preparation of vulcanized component: 15 parts of epoxy resin, 5 parts of manganese dioxide and 1 part of diphenyl hydrazine are respectively weighed in parts by weight, added to a kneader, stirred at room temperature, and uniformly passed through a three-roll mill. The vulcanized component was obtained after repeated grinding three times.
  • Step 3) The base rubber component prepared in the step 2) and the vulcanized component prepared in the step 3) are uniformly mixed and stirred at a weight ratio of 100:10 to obtain a modified nano-composite polysulfide sealant for fireproof glass, which is uniform after completion. Coated around the edge of the fireproof glass.
  • Step 1) Preparation of the base rubber component: 100 parts of the liquid polysulfide rubber and 1 part of the silane coupling agent are respectively weighed and added to the mixer, mixed and stirred for 5 minutes, and then 30 parts of nano silica is added. The mixture was kneaded for 45 minutes, the kneading temperature was 60 ° C, and the components were uniformly mixed and stirred, and then repeatedly ground for three times by a three-roll mill to obtain a base rubber component.
  • Step 2) Preparation of vulcanized component: 15 parts of epoxy resin, 5 parts of manganese dioxide and 1 part of diphenyl hydrazine are respectively weighed in parts by weight, added to a kneader, stirred at room temperature, and uniformly passed through a three-roll mill. The vulcanized component was obtained after repeated grinding three times.
  • Step 3) The base rubber component prepared in the step 2) and the vulcanized component prepared in the step 3) are uniformly mixed and stirred at a weight ratio of 100:10 to obtain a composite polysulfide sealant without modified nanometer for fireproof glass. Evenly applied around the edges of the fireproof glass.
  • Table 1 is used to determine the performance parameters of the composite polysulfide sealant for fireproof glass of each example:
  • the modified nanocomposite polysulfide sealant for fireproof glass of the present invention can significantly reduce the transmittance and effective improvement of gas and water vapor of polysulfide sealant for fireproof glass.
  • the invention also prolongs the service life of the fireproof glass, and has the advantages of simple process, easy operation and high application value.

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
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Abstract

一种防火玻璃用改性纳米复合聚硫密封胶，包括：重量比为100:5-20的基胶组份和硫化组份；所述的基胶组份包含以下重量份数：60～100份液态聚硫橡胶，0.01～5份改性纳米粉体，10～50份补强填料，0.1～5份硅烷偶联剂；所述的硫化组份包含以下重量份数：5～20份增粘剂，5～30份硫化剂，0.1～5份硫化促进剂；所述液态聚硫橡胶数均分子量为1000～4000；所述改性纳米粉体为改性白石墨烯、改性石墨烯、氧化石墨烯中的一种。改性纳米复合聚硫橡胶密封性能和机械强度增加，而其他性能则不受影响，且工艺简单，易于操作，具有较高的应用价值。

Description

[根据细则37.2由ISA制定的发明名称]　防火玻璃用改性纳米复合聚硫密封胶及其制备 技术领域
本发明涉及密封胶技术领域，具体涉及一种防火玻璃用改性纳米复合聚硫密封胶及其制备。
背景技术
随着科技和经济的发展，世界各国对建筑住宅及公用建筑物的要求越来越高，防火隔热玻璃的市场需求呈逐年上升态势，近年来防火玻璃用的粘结、密封产品多为硅酮类、聚氨酯类和聚硫密封胶。硅酮密封胶的粘结性能一般，且成本较大，聚氨酯密封胶粘结性能较好，但耐酸碱性和耐老化性能较差，而聚硫密封胶的粘结性能和耐老化性能都良好，同时成本较低，成为建筑防火玻璃中最常用的一类密封胶。
经硫化形成的聚硫密封胶通常是以液体聚硫橡胶为基体，添加适量的填料、助剂和硫化剂等经机械搅拌混合制备而成的一类密封材料。在建筑防火玻璃实际应用中，聚硫密封胶因长期受到环境中湿度、氧气、臭氧、紫外线等因素协同老化影响导致耐候性有所降低，密封胶逐渐失去弹性，与防火玻璃间的粘结力和气密性降低，导致防火玻璃层间的防火材料产生气泡，使得防火玻璃的防火、隔热性失效，一旦发生火灾将会造成巨大损失。
发明内容
有鉴于此，有必要针对上述问题，提供一种简单有效的防火玻璃用改性纳米复合聚硫密封胶及其制备。
为实现上述目的，本发明采取以下技术方案：
本发明的防火玻璃用改性纳米复合聚硫密封胶，包括：重量比为100:5-20的基胶组份和硫化组份；
所述的基胶组份包含以下重量份数：60～100份液态聚硫橡胶，0.01～5份改性纳米粉体，10～50份补强填料，0.1～5份硅烷偶联剂；
所述的硫化组份包含以下重量份数：5～20份增粘剂，5～30份硫化剂，0.1～5份硫化促进剂；
所述液态聚硫橡胶数均分子量为1000～4000；
所述改性纳米粉体为改性白石墨烯、改性石墨烯、氧化石墨烯中的一种。
作为优选的，所述基胶组份和硫化组份的重量比为100：10；所述的基胶组份包含以下重量份数：65～85份液态聚硫橡胶，0.01～3份改性纳米粉体，15～40份补强填料，0.2～3份硅烷偶联剂；
所述的硫化组份包含以下重量份数：5～15份增粘剂，6～20份硫化剂，0.1～3.5份硫化促进剂。
液态聚硫橡胶是聚硫密封胶的基体，其数均分子量大小直接决定了硫化后聚硫密封胶的机械性能，作为进一步优选，所述液态聚硫橡胶的数均分子量为3000时，具有更优的可塑性和较好的机械性能。
作为进一步优选，所述改性白石墨烯为1～10层白石墨烯经长链路易斯碱、长链路易斯酸、磺酸化物、季胺化物或非离子型表面活性剂处理，以此增加白石墨烯对基体的亲和力；所述改性石墨烯为1～10层石墨烯经聚乙烯吡咯烷酮(PVP)或十二烷基苯磺酸钠(SDBS)等表面活性剂处理，以此增加石墨烯对基体的亲和力。
作为进一步优选，所述长链路易斯碱为油胺等；所述长链路易斯酸为长链硼烷等；所述磺酸化物为十二烷基苯磺酸钠等；所述季胺化物为溴化十六烷基吡啶等；所述非离子型表面活性剂为聚环氧乙烷烷基醇酰胺等。
作为优选的，所述补强填料为纳米二氧化硅、纳米碳酸钙、炭黑中的一种；
所述硅烷偶联剂为KH-550、KH-560、KH-570中的一种；
所述增粘剂包括丙烯酸树脂、环氧树脂、甲基丙烯酸缩水甘油酯中的一种；
所述硫化剂包括过氧化钙、过氧化锌、二氧化锰中的一种；
所述促进剂为二苯胍，能加快液态聚硫橡胶室温硫化进程。
作为进一步优选，所述硫化剂为二氧化锰，是聚硫橡胶室温硫化最佳的硫化剂。
本发明防火玻璃用改性纳米复合聚硫密封胶的制备方法，包括：
步骤1)选择改性白石墨烯、改性石墨烯、氧化石墨烯中的一种作为纳米粉体；改性方法为：1-10层的白石墨烯用质量百分含量为0.1％的长链路易斯碱、长链路易斯酸、磺酸化物、季胺化物或非离子型水溶液浸泡24小时，经离心、真空干燥后得改性白石墨烯粉体；1～10层的石墨烯分散在浓度为0.1mg/ml聚乙烯吡咯烷酮或十二烷基苯磺酸钠水溶液中超声12小时，经离心、真空烘干后得改性石墨烯粉体；
步骤2)基胶组份的制备：按重量份数分别称取液态聚硫橡胶和硅烷偶联剂混合搅拌后，依次加入纳米改性粉体、补强填料，将各组份在35～100℃下混炼10-60min，多次研磨直至得到均匀的基胶组份；
步骤3)硫化组份的制备：按重量份数分别称取一定量的增粘剂、硫化剂和硫化促进剂，将各组份混合搅拌均匀得到硫化组份；
步骤4)将步骤2)制备的基胶组份和步骤3)制备的硫化组份按重量比混合搅拌均匀，即得到防火玻璃用改性纳米复合聚硫密封胶，匀涂覆于防火玻璃边缘四周可达预期的密封效果。
作为优选的，步骤2)中所述基胶组份混炼温度为60℃。
与现有技术相比，本发明的有益效果为：
改性纳米粉体选用1～10层改性白石墨烯、改性石墨烯或氧化石墨烯，片层排列紧凑、均匀，且阻挡片层数目较多，气体在聚硫橡胶中绕行，路径变长，少量添加就能很好的阻挡气体通过，增加了聚硫橡胶固化后的气密性；同时经表面活性剂处理的白石墨烯、石墨烯以及表面含有较多活性基团的氧化石墨烯，少量添加时即可达到与基体良好的润湿性，起到了补强效果，提高了聚硫橡胶的机械强度。
本发明改善了防火玻璃用聚硫密封胶因环境因素老化导致的气密性和机械强度的降低，有效保护防火玻璃内部防火液的稳定，防止防火玻璃密封的防火液中气泡的产生，使得防火玻璃的耐火、隔热性能得到了保护。本发明产品在不影响美观的前提下，延长防火玻璃的使用寿命，工艺简单，易于操作，具有较高的应用价值。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚，下面将结合本发明实施例，对本发明的技术方案作进一步清楚、完整地描述。需要说明的是，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
步骤1)纳米粉体的改性：选用1～10层的白石墨烯，用0.1％油胺水溶液浸泡24小时，经离心、真空干燥后得到白石墨烯改性粉体；
步骤2)基胶组份的制备：按重量份数分别依次称取100份液态聚硫橡胶和1份硅烷偶联剂加入到混炼机中混合搅拌5min，再依次加入0.1份步骤1)制备的改性白石墨烯粉体和30份纳米二氧化硅，混炼45min，混炼温度为40℃，各组份混合搅拌均匀后，经三辊研磨机反复研磨三遍后得到基胶组份。
步骤3)硫化组份的制备：按重量份数分别依次称取10份环氧树脂、5份二氧化锰和1份二苯胍加入到混炼机中室温混合搅拌均匀，经三辊研磨机反复研磨三遍后得到硫化组份。
步骤4)将步骤2)制备的基胶组份和步骤3)制备的硫化组份按重量比为100:6混合搅拌均匀，即得到防火玻璃用改性纳米复合聚硫密封胶，完成后均匀涂覆于防火玻璃边缘四周。
实施例2
步骤1)纳米粉体的改性：选用1～10层的白石墨烯用0.1％油胺水溶液浸泡24小时，经离心、真空干燥后得到白石墨烯改性粉体；
步骤2)基胶组份的制备：按重量份数分别依次称取100份液态聚硫橡胶和5份硅烷偶联剂加入到混炼机中混合搅拌5min，再依次加入1份步骤1)制备的改性白石墨烯粉体和10份纳米二氧化硅，混炼45min，混炼温度为80℃，各组份混合搅拌均匀后，经三辊研磨机反复研磨三遍后得到基胶组份。
步骤3)硫化组份的制备：按重量份数分别依次称取20份环氧树脂、15份二氧化锰和5份二苯胍加入到混炼机中室温混合搅拌均匀，经三辊研磨机反复研磨三遍后得到硫化组份。
步骤4)将步骤2)制备的基胶组份和步骤3)制备的硫化组份按重量比为100:15混合搅拌均匀，即得到防火玻璃用改性纳米复合聚硫密封胶，完成后均匀涂覆于防火玻璃边缘四周。
实施例3
步骤1)纳米粉体的改性：选用1～10层的白石墨烯用0.1％油胺水溶液浸泡24小时，经离心、真空干燥后得到白石墨烯改性粉体；
步骤2)基胶组份的制备：按重量份数分别依次称取100份液态聚硫橡胶和1份硅烷偶联剂加入到混炼机中混合搅拌5min，再依次加入0.3份步骤1) 制备的改性白石墨烯粉体和25份纳米二氧化硅，混炼45min，混炼温度为60℃，各组份混合搅拌均匀后，经三辊研磨机反复研磨三遍后得到基胶组份。
步骤3)硫化组份的制备：按重量份数分别依次称取15份环氧树脂、5份二氧化锰和1份二苯胍加入到混炼机中室温混合搅拌均匀，经三辊研磨机反复研磨三遍后得到硫化组份。
步骤4)将步骤2)制备的基胶组份和步骤3)制备的硫化组份按重量比100:10混合搅拌均匀，即得到防火玻璃用改性纳米复合聚硫密封胶，完成后均匀涂覆于防火玻璃边缘四周。
实施例4
步骤1)纳米粉体的改性：用1～10层的石墨烯分散在浓度为0.1mg/ml聚乙烯吡咯烷酮水溶液中超声12小时，经离心、真空烘干后得石墨烯改性粉体。
步骤2)基胶组份的制备：按重量份数分别依次称取100份液态聚硫橡胶和1份硅烷偶联剂加入到混炼机中混合搅拌5min，再依次加入0.2份步骤1)制备的改性石墨烯粉体和30份纳米二氧化硅，混炼45min，混炼温度为40℃，各组份混合搅拌均匀后，经三辊研磨机反复研磨三遍后得到基胶组份。
步骤3)硫化组份的制备：按重量份数分别依次称取10份环氧树脂、5份二氧化锰和1份二苯胍加入到混炼机中室温混合搅拌均匀，经三辊研磨机反复研磨三遍后得到硫化组份。
步骤4)将步骤2)制备的基胶组份和步骤3)制备的硫化组份按重量比为100:6混合搅拌均匀，即得到防火玻璃用改性纳米复合聚硫密封胶，完成后均匀涂覆于防火玻璃边缘四周。
实施例5
步骤1)用1～10层的石墨烯分散在浓度为0.1mg/ml聚乙烯吡咯烷酮水溶液中超声12小时，经离心、真空烘干后得石墨烯改性粉体。
步骤2)基胶组份的制备：按重量份数分别依次称取100份液态聚硫橡胶和5份硅烷偶联剂加入到混炼机中混合搅拌5min，再依次加入1份步骤1)制备的改性石墨烯粉体和10份纳米二氧化硅，混炼45min，混炼温度为80℃，各组份混合搅拌均匀后，经三辊研磨机反复研磨三遍后得到基胶组份。
步骤3)硫化组份的制备：按重量份数分别依次称取20份环氧树脂、15份二氧化锰和5份二苯胍加入到混炼机中室温混合搅拌均匀，经三辊研磨机反复研磨三遍后得到硫化组份。
步骤4)将步骤2)制备的基胶组份和步骤3)制备的硫化组份按重量比为100:15混合搅拌均匀，即得到防火玻璃用改性纳米复合聚硫密封胶，完成后均匀涂覆于防火玻璃边缘四周。
实施例6
步骤1)纳米粉体的改性：用1～10层的石墨烯分散在浓度为0.1mg/ml聚乙烯吡咯烷酮水溶液中超声12小时，经离心、真空烘干后得石墨烯改性粉体。
步骤2)基胶组份的制备：按重量份数分别依次称取100份液态聚硫橡胶和1份硅烷偶联剂加入到混炼机中混合搅拌5min，再依次加入0.5份步骤1)制备的改性石墨烯粉体和25份纳米二氧化硅，混炼45min，混炼温度为60℃，各组份混合搅拌均匀后，经三辊研磨机反复研磨三遍后得到基胶组份。
步骤3)硫化组份的制备：按重量份数分别依次称取15份环氧树脂、5份二氧化锰和1份二苯胍加入到混炼机中室温混合搅拌均匀，经三辊研磨机反复研磨三遍后得到硫化组份。
步骤4)将步骤2)制备的基胶组份和步骤3)制备的硫化组份按重量比为100:10混合搅拌均匀，即得到防火玻璃用改性纳米复合聚硫密封胶，完成后均匀涂覆于防火玻璃边缘四周。
实施例7
步骤1)基胶组份的制备：按重量份数分别依次称取100份液态聚硫橡胶和1份硅烷偶联剂加入到混炼机中混合搅拌5min，再依次加入0.1份氧化石墨烯粉体和30份纳米二氧化硅，混炼45min，混炼温度为40℃，各组份混合搅拌均匀后，经三辊研磨机反复研磨三遍后得到基胶组份。
步骤2)硫化组份的制备：按重量份数分别依次称取10份环氧树脂、5份二氧化锰和1份二苯胍加入到混炼机中室温混合搅拌均匀，经三辊研磨机反复研磨三遍后得到硫化组份。
步骤3)将步骤2)制备的基胶组份和步骤3)制备的硫化组份按重量比为100:6混合搅拌均匀，即得到防火玻璃用改性纳米复合聚硫密封胶，完成后均匀涂覆于防火玻璃边缘四周。
实施例8
步骤1)基胶组份的制备：按重量份数分别依次称取100份液态聚硫橡胶和5份硅烷偶联剂加入到混炼机中混合搅拌5min，再依次加入1份氧化石墨烯粉体和10份纳米二氧化硅，混炼45min，混炼温度为80℃，各组份混合搅拌均匀后，经三辊研磨机反复研磨三遍后得到基胶组份。
步骤2)硫化组份的制备：按重量份数分别依次称取20份环氧树脂、15份二氧化锰和5份二苯胍加入到混炼机中室温混合搅拌均匀，经三辊研磨机反复研磨三遍后得到硫化组份。
步骤3)将步骤2)制备的基胶组份和步骤3)制备的硫化组份按重量比为100:15混合搅拌均匀，即得到防火玻璃用改性纳米复合聚硫密封胶，完成后均匀涂覆于防火玻璃边缘四周。
实施例9
步骤1)基胶组份的制备：按重量份数分别依次称取100份液态聚硫橡胶和1份硅烷偶联剂加入到混炼机中混合搅拌5min，再依次加入0.4份氧化石墨 烯粉体和25份纳米二氧化硅，混炼45min，混炼温度为60℃，各组份混合搅拌均匀后，经三辊研磨机反复研磨三遍后得到基胶组份。
步骤2)硫化组份的制备：按重量份数分别依次称取15份环氧树脂、5份二氧化锰和1份二苯胍加入到混炼机中室温混合搅拌均匀，经三辊研磨机反复研磨三遍后得到硫化组份。
步骤3)将步骤2)制备的基胶组份和步骤3)制备的硫化组份按重量比为100:10混合搅拌均匀，即得到防火玻璃用改性纳米复合聚硫密封胶，完成后均匀涂覆于防火玻璃边缘四周。
对比实施例1
步骤1)基胶组份的制备：按重量份数分别依次称取100份液态聚硫橡胶和1份硅烷偶联剂加入到混炼机中混合搅拌5min，再加入30份纳米二氧化硅，混炼45min，混炼温度为60℃，各组份混合搅拌均匀后，经三辊研磨机反复研磨三遍后得到基胶组份。
步骤2)硫化组份的制备：按重量份数分别依次称取15份环氧树脂、5份二氧化锰和1份二苯胍加入到混炼机中室温混合搅拌均匀，经三辊研磨机反复研磨三遍后得到硫化组份。
步骤3)将步骤2)制备的基胶组份和步骤3)制备的硫化组份按重量比100:10混合搅拌均匀，即得到防火玻璃用无改性纳米的复合聚硫密封胶，完成后均匀涂覆于防火玻璃边缘四周。
表1中为测定各实施例防火玻璃用复合聚硫密封胶的各项性能参数：
表1各实施例复合聚硫密封胶的性能参数
Figure PCTCN2017098067-appb-000001
Figure PCTCN2017098067-appb-000002
从上表可知，与对比实施例1相比，本发明的防火玻璃用改性纳米复合聚硫密封胶，可以显著降低防火玻璃用聚硫密封胶对气体和水蒸气的透过率和有效提高机械强度。本发明还延长了防火玻璃的使用寿命，而且工艺简单，易于操作，具有很高的应用价值。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (9)

  1. 一种防火玻璃用改性纳米复合聚硫密封胶，其特征在于，包括：重量比为100:5-20的基胶组份和硫化组份；
    所述的基胶组份包含以下重量份数：60～100份液态聚硫橡胶，0.01～5份改性纳米粉体，10～50份补强填料，0.1～5份硅烷偶联剂；
    所述的硫化组份包含以下重量份数：5～20份增粘剂，5～30份硫化剂，0.1～5份硫化促进剂；
    所述液态聚硫橡胶数均分子量为1000～4000；
    所述的改性纳米粉体为改性白石墨烯、改性石墨烯、氧化石墨烯中的一种。
  2. 根据权利要求1所述的防火玻璃用改性纳米复合聚硫密封胶，其特征在于，所述基胶组份和硫化组份的重量比为100：10；
    所述的基胶组份包含以下重量份数：65～85份液态聚硫橡胶，0.01～3份改性纳米粉体，15～40份补强填料，0.2～3份硅烷偶联剂；
    所述的硫化组份包含以下重量份数：5～15份增粘剂，6～20份硫化剂，0.1～3.5份硫化促进剂。
  3. 根据权利要求1或2所述的防火玻璃用改性纳米复合聚硫密封胶，其特征在于，所述液态聚硫橡胶的数均分子量为3000。
  4. 根据权利要求1或2所述的防火玻璃用改性纳米复合聚硫密封胶，其特征在于，所述改性白石墨烯为1～10层白石墨烯经长链路易斯碱、长链路易斯酸、磺酸化物、季胺化物或非离子型表面活性剂处理；所述改性石墨烯为1～10层石墨烯经聚乙烯吡咯烷酮(PVP)或十二烷基苯磺酸钠(SDBS)表面活性剂处理。
  5. 根据权利要求4所述的防火玻璃用改性纳米复合聚硫密封胶，其特征在于，所述长链路易斯碱为油胺；所述长链路易斯酸为长链硼烷；所述磺酸化物 为十二烷基苯磺酸钠；所述季胺化物为溴化十六烷基吡啶；所述非离子型表面活性剂为聚环氧乙烷烷基醇酰胺。
  6. 根据权利要求1或2所述的防火玻璃用改性纳米复合聚硫密封胶，其特征在于，所述补强填料为纳米二氧化硅、纳米碳酸钙、炭黑中的一种；
    所述硅烷偶联剂为KH-550、KH-560、KH-570中的一种；
    所述增粘剂包括丙烯酸树脂、环氧树脂、甲基丙烯酸缩水甘油酯中的一种；
    所述硫化剂包括过氧化钙、过氧化锌、二氧化锰中的一种；
    所述促进剂为二苯胍。
  7. 根据权利要求6所述的防火玻璃用改性纳米复合聚硫密封胶，其特征在于，所述硫化剂为二氧化锰。
  8. 一种权利要求1或2所述的防火玻璃用改性纳米复合聚硫密封胶的制备方法，其特征在于，包括：
    步骤1)选择改性白石墨烯、改性石墨烯、氧化石墨烯中的一种作为纳米粉体；改性方法为：1-10层的白石墨烯用质量百分含量为0.1％的长链路易斯碱、长链路易斯酸、磺酸化物、季胺化物或非离子型表面活性剂水溶液浸泡24小时，经离心、真空干燥后得改性白石墨烯粉体；1～10层的石墨烯分散在浓度为0.1mg/ml聚乙烯吡咯烷酮或十二烷基苯磺酸钠水溶液中超声12小时，经离心、真空烘干后得改性石墨烯粉体；
    步骤2)基胶组份的制备：按重量份数分别称取液态聚硫橡胶和硅烷偶联剂混合搅拌后，依次加入纳米改性粉体、补强填料，将各组份在35～100℃下混炼10-60min，多次研磨直至得到均匀的基胶组份；
    步骤3)硫化组份的制备：按重量份数分别称取一定量的增粘剂、硫化剂和硫化促进剂，将各组份混合搅拌均匀得到硫化组份；
    步骤4)将步骤2)制备的基胶组份和步骤3)制备的硫化组份按 重量比混合搅拌均匀，，即得到防火玻璃用改性纳米复合聚硫密封胶，匀涂覆于防火玻璃边缘四周可达预期的密封效果。
  9. 根据权利要求8所述的防火玻璃用改性纳米复合聚硫密封胶的制备方法，其特征在于，步骤2)中所述基胶组份混炼温度为60℃。
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113087905A (zh) * 2021-04-30 2021-07-09 郑州中原思蓝德高科股份有限公司 一种巯端基聚合物及其制备方法、聚硫密封胶
CN113185149A (zh) * 2021-06-08 2021-07-30 中国科学院长春应用化学研究所 一种防火玻璃及其制备方法
CN113372873A (zh) * 2021-06-30 2021-09-10 快思瑞科技(上海)有限公司 双组分聚硫密封胶组合物、双组分聚硫密封胶及制备方法
CN113493671A (zh) * 2021-06-30 2021-10-12 快思瑞科技(上海)有限公司 单组分聚硫密封胶组合物、单组分聚硫密封胶及制备方法
CN113754972A (zh) * 2020-06-01 2021-12-07 临沂市海纳电子有限公司 一种飞机发动机电缆材料及制作方法
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CN114854362A (zh) * 2022-04-14 2022-08-05 河南金欧特实业集团股份有限公司 沥青路面高性能净味速熔密封胶
CN117659933A (zh) * 2023-12-07 2024-03-08 杭州之江有机硅化工有限公司 一种聚硫密封胶及其制备方法和应用

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106244089B (zh) * 2016-08-22 2019-05-14 广东纳路纳米科技有限公司 一种防火玻璃用改性纳米复合聚硫密封胶及其制备
CN109180938A (zh) * 2018-08-31 2019-01-11 王雪峰 一种抗冲击高粘结性聚硫橡胶的制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102329595A (zh) * 2011-08-10 2012-01-25 浙江大学 一种高强度聚硫密封胶
CN102838964A (zh) * 2012-08-29 2012-12-26 浙江大学 一种高耐候性聚硫密封胶
WO2013165846A1 (en) * 2012-05-03 2013-11-07 Prc-Desoto International, Inc. Compositions with a sulfur-containing polymer and graphenic carbon particles
CN106244089A (zh) * 2016-08-22 2016-12-21 广东纳路纳米科技有限公司 一种防火玻璃用改性纳米复合聚硫密封胶及其制备

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008133399A (ja) * 2006-11-29 2008-06-12 Yokohama Rubber Co Ltd:The ポリサルファイド接着剤組成物
CN101575493B (zh) * 2009-06-18 2011-09-21 郑州中原应用技术研究开发有限公司 双组分聚硫防火阻燃密封胶及其制备方法
CN102277125B (zh) * 2011-08-31 2013-09-18 辽宁双强塑胶科技开发有限公司 阻燃型聚硫密封胶及其制备方法
CN102382606B (zh) * 2011-09-19 2013-10-30 常州合润新材料科技有限公司 一种填充石墨烯各向同性高性能导电胶及其制备方法
CN102583335B (zh) * 2012-01-19 2014-03-12 常州大学 一种石墨烯均匀分散液的制备方法
CN102618207B (zh) * 2012-03-28 2013-08-21 黑龙江省科学院石油化学研究院 一种双组分聚硫密封剂及其制备方法
CN104387771A (zh) * 2014-11-03 2015-03-04 中国航空工业集团公司北京航空材料研究院 一种双组份导电聚硫密封剂及其制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102329595A (zh) * 2011-08-10 2012-01-25 浙江大学 一种高强度聚硫密封胶
WO2013165846A1 (en) * 2012-05-03 2013-11-07 Prc-Desoto International, Inc. Compositions with a sulfur-containing polymer and graphenic carbon particles
CN102838964A (zh) * 2012-08-29 2012-12-26 浙江大学 一种高耐候性聚硫密封胶
CN106244089A (zh) * 2016-08-22 2016-12-21 广东纳路纳米科技有限公司 一种防火玻璃用改性纳米复合聚硫密封胶及其制备

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113754972A (zh) * 2020-06-01 2021-12-07 临沂市海纳电子有限公司 一种飞机发动机电缆材料及制作方法
CN113087905A (zh) * 2021-04-30 2021-07-09 郑州中原思蓝德高科股份有限公司 一种巯端基聚合物及其制备方法、聚硫密封胶
CN113087905B (zh) * 2021-04-30 2022-09-16 郑州中原思蓝德高科股份有限公司 一种巯端基聚合物及其制备方法、聚硫密封胶
CN113185149A (zh) * 2021-06-08 2021-07-30 中国科学院长春应用化学研究所 一种防火玻璃及其制备方法
CN113372873A (zh) * 2021-06-30 2021-09-10 快思瑞科技(上海)有限公司 双组分聚硫密封胶组合物、双组分聚硫密封胶及制备方法
CN113493671A (zh) * 2021-06-30 2021-10-12 快思瑞科技(上海)有限公司 单组分聚硫密封胶组合物、单组分聚硫密封胶及制备方法
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CN114854362B (zh) * 2022-04-14 2023-08-15 河南金欧特实业集团股份有限公司 沥青路面高性能净味速熔密封胶
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