CN105400116A - Highly flame-retardant and ageing-resistant polyvinyl chloride composite for automobile rubber pipe - Google Patents
Highly flame-retardant and ageing-resistant polyvinyl chloride composite for automobile rubber pipe Download PDFInfo
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Abstract
The invention discloses a highly flame-retardant and ageing-resistant polyvinyl chloride composite for an automobile rubber pipe. The raw materials of the highly flame-retardant and ageing-resistant polyvinyl chloride composite comprise the following components: rare-earth modified polyvinyl chloride, polyvinylidene fluoride, carboxylic butadiene-styrene latex, polyurethane elastomer, polyvinyl butyral, an acrylonitrile-butadiene-styrene copolymer, nano-zinc oxide, magnesium hydrate, aluminium hydroxide, pentaerythritol, nano calcium carbonate, talcum opwder, zinc borate, isopropyl phenyl diphenyl phosphate, zinc nitrilotiracetate, calcium nitrilotiracetate, stearic acid, epoxidized soybean oil, polyethylene wax, a phosphite antioxidant, triallyl cyanurate, a silane coupling agent and nanometer yttrium oxide. The highly flame-retardant and ageing-resistant polyvinyl chloride composite for the automobile rubber pipe, provided by the invention, is good in heat resistance and excellent in ageing resistance and flame resistance and the automobile rubber pipe made of the highly flame-retardant and ageing-resistant polyvinyl chloride composite is long in service life.
Description
Technical field
The present invention relates to polyvinyl chloride technical field, particularly relate to the ageing-resistant polyvinyl chloride composite materials of a kind of automotive hose high flame retardant.
Background technology
Polyvinyl chloride is a kind of broad-spectrum general-purpose plastics, and it is with low cost, convenient formation.As macromolecular material, it has good physical and mechanical properties, electric property and resistance to chemical corrosion, and output is large, inexpensive and by suitable batching and various method for processing forming can make a series of by soft to multiple plastics that are hard, different properties, be widely used in the fields such as building, light industry, chemical industry, electrical equipment, electric wire at present.Pvc material is also one of material that automotive hose is conventional, but in actual applications, pvc material also exists poor heat resistance, it is yielding to be heated, ageing resistance and flame retardant resistance are not very desirable shortcomings, limit its application in automotive hose field, physical and chemical modified must be carried out by multiple method to it.
Summary of the invention
Based on the technical problem that background technology exists, the present invention proposes the ageing-resistant polyvinyl chloride composite materials of a kind of automotive hose high flame retardant, its good heat resistance, ageing resistance and excellent fireproof performance, the automotive hose long service life made of it.
The ageing-resistant polyvinyl chloride composite materials of a kind of automotive hose high flame retardant that the present invention proposes, its raw material comprises following component by weight: rare earth modified polyvinyl chloride 100 parts, polyvinylidene difluoride (PVDF) 5-20 part, carboxylic styrene butadiene latex 5-12 part, polyurethane elastomer 3-10 part, polyvinyl butyral acetal 2-10 part, acrylonitrile-butadiene-styrene copolymer 1-5 part, nano zine oxide 3-10 part, magnesium hydroxide 2-8 part, aluminium hydroxide 3-12 part, tetramethylolmethane 5-15 part, nano-calcium carbonate 2-10 part, talcum powder 3-15 part, zinc borate 3-15 part, tricresyl phosphate isopropyl phenyl ester 5-12 part, zinc nitrilotiracetate 2-4 part, nitrilotriacetic acid(NTA) calcium 3-5 part, stearic acid 2-5 part, epoxy soybean oil 1-5 part, polyethylene wax 2-5 part, phosphite ester kind antioxidant 0.2-0.5 part, triallyl cyanurate 0.2-1 part, silane coupling agent 2-5 part, nano yttrium oxide 1-5 part.
Preferably, its raw material comprises following component by weight: rare earth modified polyvinyl chloride 100 parts, polyvinylidene difluoride (PVDF) 12-15 part, carboxylic styrene butadiene latex 8-10 part, polyurethane elastomer 5.8-7 part, polyvinyl butyral acetal 5.9-7 part, acrylonitrile-butadiene-styrene copolymer 3.2-4 part, nano zine oxide 6-8.5 part, magnesium hydroxide 5.8-6.2 part, aluminium hydroxide 7-9 part, tetramethylolmethane 10-12 part, nano-calcium carbonate 5.5-6.3 part, talcum powder 8-11 part, zinc borate 7-10 part, tricresyl phosphate isopropyl phenyl ester 8-9.5 part, zinc nitrilotiracetate 2.9-3.4 part, nitrilotriacetic acid(NTA) calcium 3.8-4.2 part, stearic acid 3-3.6 part, epoxy soybean oil 3.2-4 part, polyethylene wax 3.5-4 part, phosphite ester kind antioxidant 0.3-0.5 part, triallyl cyanurate 0.5-0.8 part, silane coupling agent 2.8-3.5 part, nano yttrium oxide 3.2-4 part.
Preferably, its raw material comprises following component by weight: rare earth modified polyvinyl chloride 100 parts, polyvinylidene difluoride (PVDF) 13 parts, carboxylic styrene butadiene latex 9 parts, polyurethane elastomer 6.5 parts, polyvinyl butyral acetal 6.3 parts, acrylonitrile-butadiene-styrene copolymer 3.8 parts, nano zine oxide 7 parts, magnesium hydroxide 6 parts, 8 parts, aluminium hydroxide, tetramethylolmethane 11 parts, nano-calcium carbonate 6 parts, talcum powder 9 parts, zinc borate 8.5 parts, tricresyl phosphate isopropyl phenyl ester 9.2 parts, zinc nitrilotiracetate 3 parts, nitrilotriacetic acid(NTA) calcium 4.2 parts, stearic acid 3.2 parts, epoxy soybean oil 3.6 parts, polyethylene wax 3.8 parts, phosphite ester kind antioxidant 0.34 part, triallyl cyanurate 0.7 part, silane coupling agent 3 parts, nano yttrium oxide 3.8 parts.
Preferably, described rare earth modified polyvinyl chloride is prepared according to following technique: add in 30-50 part dimethylbenzene by 30-50 part nano yttrium oxide by weight, 10-20 part methacrylic acid is added after stirring, 35-50min is reacted at 65-80 DEG C, then temperature is regulated to be 95-100 DEG C, reaction 1.5-2h, room temperature is cooled to after reaction terminates, then 25-50 part polyvinyl chloride and 50-100 part tetrahydrofuran (THF) is added, 20-35min is stirred at 45-60 DEG C, then 0.5-2 part ammonium persulphate is added, reaction 3-5h, reaction terminates rear toluene extracting, then drying obtains described rare earth modified polyvinyl chloride.
Preferably, described rare earth modified polyvinyl chloride is prepared according to following technique: add in 40 parts of dimethylbenzene by 38 parts of nano yttrium oxides by weight, 15 parts of methacrylic acids are added after stirring, 40min is reacted at 67 DEG C, then temperature is regulated to be 98 DEG C, reaction 1.7h, room temperature is cooled to after reaction terminates, then 35 parts of polyvinyl chloride and 70 parts of tetrahydrofuran (THF)s are added, at 55 DEG C, stir 30min, then add 1.3 parts of ammonium persulphates, reaction 4h, reaction terminates rear toluene extracting, and then drying obtains described rare earth modified polyvinyl chloride;
Preferably, in the preparation process of rare earth modified polyvinyl chloride, the median size of described nano yttrium oxide is 65-86nm.
Preferably, the median size of described nano zine oxide is 10-35nm; The median size of described nano-calcium carbonate is 15-40nm.
Have selected rare earth modified polyvinyl chloride in the present invention is major ingredient, give the thermotolerance of matrix material excellence, ageing resistance and flame retardant resistance, in optimal way, in the preparation process of rare earth modified polyvinyl chloride, first have selected nano yttrium oxide and methacrylic acid reacts, obtain methacrylic acid yttrium, after mixing with polyvinyl chloride, under the initiation of ammonium persulphate, heat-staple methacrylic acid yttrium has been grafted in polyvinyl chloride molecule, on the one hand, define the 3 D cross-linked structure centered by rare earth ion, the conformation of polyvinyl chloride molecule is made to be transformed to the large isotaxy of stability from the syndiotaxy of the little flat serrations formula of stability, effectively prevent the formation of long conjugated polyene, thus improve the decomposition temperature of polyvinyl chloride, improve thermostability and the ageing resistance of rare earth modified polyvinyl chloride, on the other hand, methacrylic acid yttrium can as the absorption agent of HCl, to make on rare earth modified polyvinyl chloride molecular chain self with can effectively improve heat-staple segment, further improve thermostability and the ageing resistance of polyvinyl chloride molecule, coordinate the polyvinylidene difluoride (PVDF) that rare earth modified polyvinyl chloride adds, carboxylic styrene butadiene latex, polyurethane elastomer, polyvinyl butyral acetal, acrylonitrile-butadiene-styrene copolymer and rare earth modified polyvinyl chloride have good consistency, by regulating the content of each material, its performance is worked in coordination with, on the one hand, with nano-calcium carbonate, talcum powder and tricresyl phosphate isopropyl phenyl ester coordinate, improve and add the large defect of the polyvinyl chloride fragility that causes because of rare earth ion, on the other hand, improve the thermotolerance of system, physical strength, ultraviolet resistance, processibility, wear resistance, improve the ageing resistance of matrix material, nano zine oxide, magnesium hydroxide, aluminium hydroxide, nano-calcium carbonate, talcum powder, zinc borate, nano yttrium oxide add in system by aforementioned proportion, silane coupling agent auxiliary under, be uniformly dispersed in system, good with the consistency of system, coordinate with tetramethylolmethane, tricresyl phosphate isopropyl phenyl ester on the one hand, give the flame retardant resistance of matrix material excellence, the oxygen index of matrix material is made to reach more than 42, on the other hand, coordinate with nano yttrium oxide and phosphite ester kind antioxidant, improve the thermotolerance of matrix material, ageing resistance and physical strength, triallyl cyanurate adds in system and has crosslinked effect, further increases the flame retardant resistance of matrix material while improving system intensity.
Performance Detection is carried out to the ageing-resistant polyvinyl chloride composite materials of automotive hose high flame retardant of the present invention, its tensile strength >=18.9MPa, elongation at break >=450%; After 136 DEG C × 168h is aging, tensile strength retention rate >=92.3%, reserved elongation at break >=93.4%.
Embodiment
Below, by specific embodiment, technical scheme of the present invention is described in detail.
Embodiment 1
The ageing-resistant polyvinyl chloride composite materials of a kind of automotive hose high flame retardant that the present invention proposes, its raw material comprises following component by weight: rare earth modified polyvinyl chloride 100 parts, polyvinylidene difluoride (PVDF) 5 parts, carboxylic styrene butadiene latex 12 parts, polyurethane elastomer 3 parts, polyvinyl butyral acetal 10 parts, acrylonitrile-butadiene-styrene copolymer 1 part, nano zine oxide 10 parts, magnesium hydroxide 2 parts, 12 parts, aluminium hydroxide, tetramethylolmethane 5 parts, nano-calcium carbonate 10 parts, talcum powder 3 parts, zinc borate 15 parts, tricresyl phosphate isopropyl phenyl ester 5 parts, zinc nitrilotiracetate 4 parts, nitrilotriacetic acid(NTA) calcium 3 parts, stearic acid 5 parts, epoxy soybean oil 1 part, polyethylene wax 5 parts, phosphite ester kind antioxidant 0.2 part, triallyl cyanurate 1 part, silane coupling agent 2 parts, nano yttrium oxide 1 part.
Embodiment 2
The ageing-resistant polyvinyl chloride composite materials of a kind of automotive hose high flame retardant that the present invention proposes, its raw material comprises following component by weight: rare earth modified polyvinyl chloride 100 parts, polyvinylidene difluoride (PVDF) 20 parts, carboxylic styrene butadiene latex 5 parts, polyurethane elastomer 10 parts, polyvinyl butyral acetal 2 parts, acrylonitrile-butadiene-styrene copolymer 5 parts, nano zine oxide 3 parts, magnesium hydroxide 8 parts, 3 parts, aluminium hydroxide, tetramethylolmethane 15 parts, nano-calcium carbonate 2 parts, talcum powder 15 parts, zinc borate 3 parts, tricresyl phosphate isopropyl phenyl ester 12 parts, zinc nitrilotiracetate 2 parts, nitrilotriacetic acid(NTA) calcium 5 parts, stearic acid 2 parts, epoxy soybean oil 5 parts, polyethylene wax 2 parts, phosphite ester kind antioxidant 0.5 part, triallyl cyanurate 0.2 part, silane coupling agent 5 parts, nano yttrium oxide 5 parts.
Embodiment 3
The ageing-resistant polyvinyl chloride composite materials of a kind of automotive hose high flame retardant that the present invention proposes, its raw material comprises following component by weight: rare earth modified polyvinyl chloride 100 parts, polyvinylidene difluoride (PVDF) 12 parts, carboxylic styrene butadiene latex 10 parts, polyurethane elastomer 5.8 parts, polyvinyl butyral acetal 7 parts, acrylonitrile-butadiene-styrene copolymer 3.2 parts, nano zine oxide 8.5 parts, magnesium hydroxide 5.8 parts, 9 parts, aluminium hydroxide, tetramethylolmethane 12 parts, nano-calcium carbonate 6.3 parts, talcum powder 8 parts, zinc borate 10 parts, tricresyl phosphate isopropyl phenyl ester 8 parts, zinc nitrilotiracetate 3.4 parts, nitrilotriacetic acid(NTA) calcium 3.8 parts, stearic acid 3.6 parts, epoxy soybean oil 3.2 parts, polyethylene wax 4 parts, phosphite ester kind antioxidant 0.3 part, triallyl cyanurate 0.8 part, silane coupling agent 2.8 parts, nano yttrium oxide 4 parts,
Wherein, the median size of described nano zine oxide is 10nm; The median size of described nano-calcium carbonate is 40nm;
Described rare earth modified polyvinyl chloride is prepared according to following technique: add in 30 parts of dimethylbenzene by 50 parts of nano yttrium oxides by weight, 20 parts of methacrylic acids are added after stirring, 35min is reacted at 65 DEG C, then temperature is regulated to be 100 DEG C, reaction 1.5h, room temperature is cooled to after reaction terminates, then 25 parts of polyvinyl chloride and 100 parts of tetrahydrofuran (THF)s are added, 20min is stirred at 60 DEG C, then 2 parts of ammonium persulphates are added, reaction 3h, reaction terminates rear toluene extracting, and then drying obtains described rare earth modified polyvinyl chloride; Wherein, the median size of described nano yttrium oxide is 80nm.
Embodiment 4
The ageing-resistant polyvinyl chloride composite materials of a kind of automotive hose high flame retardant that the present invention proposes, its raw material comprises following component by weight: rare earth modified polyvinyl chloride 100 parts, polyvinylidene difluoride (PVDF) 15 parts, carboxylic styrene butadiene latex 8 parts, polyurethane elastomer 7 parts, polyvinyl butyral acetal 5.9 parts, acrylonitrile-butadiene-styrene copolymer 4 parts, nano zine oxide 6 parts, magnesium hydroxide 6.2 parts, 7 parts, aluminium hydroxide, tetramethylolmethane 10 parts, nano-calcium carbonate 5.5 parts, talcum powder 11 parts, zinc borate 7 parts, tricresyl phosphate isopropyl phenyl ester 9.5 parts, zinc nitrilotiracetate 2.9 parts, nitrilotriacetic acid(NTA) calcium 4.2 parts, stearic acid 3 parts, epoxy soybean oil 4 parts, polyethylene wax 3.5 parts, phosphite ester kind antioxidant 0.5 part, triallyl cyanurate 0.5 part, silane coupling agent 3.5 parts, nano yttrium oxide 3.2 parts,
Wherein, the median size of described nano zine oxide is 35nm; The median size of described nano-calcium carbonate is 15nm;
Described rare earth modified polyvinyl chloride is prepared according to following technique: add in 50 parts of dimethylbenzene by 30 parts of nano yttrium oxides by weight, 10 parts of methacrylic acids are added after stirring, 50min is reacted at 80 DEG C, then temperature is regulated to be 95 DEG C, reaction 2h, room temperature is cooled to after reaction terminates, then 50 parts of polyvinyl chloride and 50 parts of tetrahydrofuran (THF)s are added, 35min is stirred at 45 DEG C, then 0.5 part of ammonium persulphate is added, reaction 5h, reaction terminates rear toluene extracting, and then drying obtains described rare earth modified polyvinyl chloride; Wherein, the median size of described nano yttrium oxide is 86nm.
Embodiment 5
The ageing-resistant polyvinyl chloride composite materials of a kind of automotive hose high flame retardant that the present invention proposes, its raw material comprises following component by weight: rare earth modified polyvinyl chloride 100 parts, polyvinylidene difluoride (PVDF) 13 parts, carboxylic styrene butadiene latex 9 parts, polyurethane elastomer 6.5 parts, polyvinyl butyral acetal 6.3 parts, acrylonitrile-butadiene-styrene copolymer 3.8 parts, nano zine oxide 7 parts, magnesium hydroxide 6 parts, 8 parts, aluminium hydroxide, tetramethylolmethane 11 parts, nano-calcium carbonate 6 parts, talcum powder 9 parts, zinc borate 8.5 parts, tricresyl phosphate isopropyl phenyl ester 9.2 parts, zinc nitrilotiracetate 3 parts, nitrilotriacetic acid(NTA) calcium 4.2 parts, stearic acid 3.2 parts, epoxy soybean oil 3.6 parts, polyethylene wax 3.8 parts, phosphite ester kind antioxidant 0.34 part, triallyl cyanurate 0.7 part, silane coupling agent 3 parts, nano yttrium oxide 3.8 parts,
Wherein, the median size of described nano zine oxide is 30nm; The median size of described nano-calcium carbonate is 20nm;
Described rare earth modified polyvinyl chloride is prepared according to following technique: add in 40 parts of dimethylbenzene by 38 parts of nano yttrium oxides by weight, 15 parts of methacrylic acids are added after stirring, 40min is reacted at 67 DEG C, then temperature is regulated to be 98 DEG C, reaction 1.7h, room temperature is cooled to after reaction terminates, then 35 parts of polyvinyl chloride and 70 parts of tetrahydrofuran (THF)s are added, 30min is stirred at 55 DEG C, then 1.3 parts of ammonium persulphates are added, reaction 4h, reaction terminates rear toluene extracting, and then drying obtains described rare earth modified polyvinyl chloride; Wherein, the median size of described nano yttrium oxide is 65nm.
The above; be only the present invention's preferably embodiment; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to according to technical scheme of the present invention and inventive concept thereof and replace or change, all should be encompassed within protection scope of the present invention.
Claims (7)
1. the ageing-resistant polyvinyl chloride composite materials of automotive hose high flame retardant, it is characterized in that, its raw material comprises following component by weight: rare earth modified polyvinyl chloride 100 parts, polyvinylidene difluoride (PVDF) 5-20 part, carboxylic styrene butadiene latex 5-12 part, polyurethane elastomer 3-10 part, polyvinyl butyral acetal 2-10 part, acrylonitrile-butadiene-styrene copolymer 1-5 part, nano zine oxide 3-10 part, magnesium hydroxide 2-8 part, aluminium hydroxide 3-12 part, tetramethylolmethane 5-15 part, nano-calcium carbonate 2-10 part, talcum powder 3-15 part, zinc borate 3-15 part, tricresyl phosphate isopropyl phenyl ester 5-12 part, zinc nitrilotiracetate 2-4 part, nitrilotriacetic acid(NTA) calcium 3-5 part, stearic acid 2-5 part, epoxy soybean oil 1-5 part, polyethylene wax 2-5 part, phosphite ester kind antioxidant 0.2-0.5 part, triallyl cyanurate 0.2-1 part, silane coupling agent 2-5 part, nano yttrium oxide 1-5 part.
2. the ageing-resistant polyvinyl chloride composite materials of automotive hose high flame retardant according to claim 1, it is characterized in that, its raw material comprises following component by weight: rare earth modified polyvinyl chloride 100 parts, polyvinylidene difluoride (PVDF) 12-15 part, carboxylic styrene butadiene latex 8-10 part, polyurethane elastomer 5.8-7 part, polyvinyl butyral acetal 5.9-7 part, acrylonitrile-butadiene-styrene copolymer 3.2-4 part, nano zine oxide 6-8.5 part, magnesium hydroxide 5.8-6.2 part, aluminium hydroxide 7-9 part, tetramethylolmethane 10-12 part, nano-calcium carbonate 5.5-6.3 part, talcum powder 8-11 part, zinc borate 7-10 part, tricresyl phosphate isopropyl phenyl ester 8-9.5 part, zinc nitrilotiracetate 2.9-3.4 part, nitrilotriacetic acid(NTA) calcium 3.8-4.2 part, stearic acid 3-3.6 part, epoxy soybean oil 3.2-4 part, polyethylene wax 3.5-4 part, phosphite ester kind antioxidant 0.3-0.5 part, triallyl cyanurate 0.5-0.8 part, silane coupling agent 2.8-3.5 part, nano yttrium oxide 3.2-4 part.
3. the ageing-resistant polyvinyl chloride composite materials of automotive hose high flame retardant according to claim 1 or 2, it is characterized in that, its raw material comprises following component by weight: rare earth modified polyvinyl chloride 100 parts, polyvinylidene difluoride (PVDF) 13 parts, carboxylic styrene butadiene latex 9 parts, polyurethane elastomer 6.5 parts, polyvinyl butyral acetal 6.3 parts, acrylonitrile-butadiene-styrene copolymer 3.8 parts, nano zine oxide 7 parts, magnesium hydroxide 6 parts, 8 parts, aluminium hydroxide, tetramethylolmethane 11 parts, nano-calcium carbonate 6 parts, talcum powder 9 parts, zinc borate 8.5 parts, tricresyl phosphate isopropyl phenyl ester 9.2 parts, zinc nitrilotiracetate 3 parts, nitrilotriacetic acid(NTA) calcium 4.2 parts, stearic acid 3.2 parts, epoxy soybean oil 3.6 parts, polyethylene wax 3.8 parts, phosphite ester kind antioxidant 0.34 part, triallyl cyanurate 0.7 part, silane coupling agent 3 parts, nano yttrium oxide 3.8 parts.
4. the ageing-resistant polyvinyl chloride composite materials of automotive hose high flame retardant according to any one of claim 1-3, it is characterized in that, described rare earth modified polyvinyl chloride is prepared according to following technique: add in 30-50 part dimethylbenzene by 30-50 part nano yttrium oxide by weight, 10-20 part methacrylic acid is added after stirring, 35-50min is reacted at 65-80 DEG C, then temperature is regulated to be 95-100 DEG C, reaction 1.5-2h, room temperature is cooled to after reaction terminates, then 25-50 part polyvinyl chloride and 50-100 part tetrahydrofuran (THF) is added, 20-35min is stirred at 45-60 DEG C, then 0.5-2 part ammonium persulphate is added, reaction 3-5h, reaction terminates rear toluene extracting, then drying obtains described rare earth modified polyvinyl chloride.
5. the ageing-resistant polyvinyl chloride composite materials of automotive hose high flame retardant according to any one of claim 1-4, it is characterized in that, described rare earth modified polyvinyl chloride is prepared according to following technique: add in 40 parts of dimethylbenzene by 38 parts of nano yttrium oxides by weight, 15 parts of methacrylic acids are added after stirring, 40min is reacted at 67 DEG C, then temperature is regulated to be 98 DEG C, reaction 1.7h, room temperature is cooled to after reaction terminates, then 35 parts of polyvinyl chloride and 70 parts of tetrahydrofuran (THF)s are added, 30min is stirred at 55 DEG C, then 1.3 parts of ammonium persulphates are added, reaction 4h, reaction terminates rear toluene extracting, then drying obtains described rare earth modified polyvinyl chloride.
6. the ageing-resistant polyvinyl chloride composite materials of automotive hose high flame retardant according to claim 4 or 5, is characterized in that, in the preparation process of rare earth modified polyvinyl chloride, the median size of described nano yttrium oxide is 65-86nm.
7. the ageing-resistant polyvinyl chloride composite materials of automotive hose high flame retardant according to any one of claim 1-6, is characterized in that, the median size of described nano zine oxide is 10-35nm; The median size of described nano-calcium carbonate is 15-40nm.
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Application publication date: 20160316 |