CN108102252A - A kind of heat-resisting PVC resin and preparation method thereof - Google Patents
A kind of heat-resisting PVC resin and preparation method thereof Download PDFInfo
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- CN108102252A CN108102252A CN201711402815.2A CN201711402815A CN108102252A CN 108102252 A CN108102252 A CN 108102252A CN 201711402815 A CN201711402815 A CN 201711402815A CN 108102252 A CN108102252 A CN 108102252A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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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
- C08K3/32—Phosphorus-containing compounds
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- C08K2003/327—Aluminium phosphate
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
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- C08K2003/385—Binary compounds of nitrogen with boron
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention discloses a kind of heat-resisting PVC resins, belong to resin making technique field, the heat-resisting PVC resin, including following raw material：Corvic, end hydroxy butadiene, polyphenylene sulfide, methacrylic acid, epoxy resin E 51, coumarone indene resin, isocyanates, polyphosphate, butylene terephthalate, hydrogenated styrene, low density polyethylene (LDPE), nano-ceramic powder, nm-class boron nitride, zinc borate, aluminium triphosphate, nano aluminium oxide, calcium sulfate crystal whiskers, chlorinated paraffin, micaceous iron oxide, pine tar, polyadipate, benzotriazole, aluminum diethylphosphinate, antimony oxide, kodalk, silane coupling agent KH 560, heat resistance modified auxiliary agent, the heat-resisting PVC resin is by preparing base-material, prepare modified materials, and by base-material, the materials such as modified materials mixing and etc. made of.The Corvic that the present invention is prepared has excellent heat resistance.
Description
Technical field
The present invention relates to the technical field of resin preparation process more particularly to a kind of heat-resisting PVC resin and its preparations
Method.
Background technology
Corvic main ingredient is polyvinyl chloride, additionally incorporates other compositions to enhance its heat resistance, toughness is prolonged
Malleability etc..It is liked deeply in the world today, a kind of rather popular and synthetic material for being also widely used.Its whole world
Usage amount is in second in various synthetic materials.
A kind of Chinese patent application document " Corvic and its preparation method and application (application publication number：
CN101143954A a kind of Corvic) " is disclosed, described Corvic is counted, in parts by weight by including
100 number Corvics, 0.5-1.5 parts of ultrafine inorganic powders, 0.5-5 parts of stabilizers, 1-4 parts of modifiers, 0.1-2
Part lubricant, 0-20 parts of impact modifying agents and 0-4 parts of plasticizer are raw material, are made after 170-190 DEG C of melt blending.It is prepared into
The Corvic arrived is equal by the titanium dioxide or silicon dioxide powder physical efficiency of the ultra-fine load silver ion of organic modification
Even to be dispersed in Corvic, making gained polyvinyl chloride resin modification resin, not only mechanical property improves a lot, and simultaneous
Standby anti-microbial property, but the needs of its heat resistance can not meet in actual use.
The content of the invention
To solve technical problem present in background technology, the present invention proposes a kind of heat-resisting PVC resin and its preparation
Method, to solve in a kind of Chinese patent application document " Corvic and its preparation method and application (application publication number：
CN101143954A the problem of Corvic heat resistance is insufficient disclosed in) ".
A kind of heat-resisting PVC resin proposed by the present invention, including following raw material：The poly- fourth of Corvic, terminal hydroxy group
Diene, polyphenylene sulfide, methacrylic acid, epoxy resin E-51, coumarone indene resin, isocyanates, polyphosphate, terephthalic acid (TPA)
Fourth diester, hydrogenated styrene, low density polyethylene (LDPE), nano-ceramic powder, nm-class boron nitride, zinc borate, aluminium triphosphate, nano oxygen
Change aluminium, calcium sulfate crystal whiskers, chlorinated paraffin, micaceous iron oxide, pine tar, polyadipate, benzotriazole, diethyl phosphinic acids
Aluminium, antimony oxide, kodalk, silane coupling agent KH-560, heat resistance modified auxiliary agent；
The aluminum diethylphosphinate, antimony oxide, kodalk, silane coupling agent KH-560, heat resistance modified auxiliary agent
Weight ratio be (4-6)：(8-10)：(5-8)：(2-4)：(8-16).
Further, the aluminum diethylphosphinate, antimony oxide, kodalk, silane coupling agent KH-560, heat-resisting
The weight ratio of modified additive is 5：9：6.5：3：12.
Further, in units of parts by weight, including following raw material：40-50 parts of Corvic, terminal hydroxy group polybutadiene
It is 15-25 parts of alkene, 5-15 parts of polyphenylene sulfide, 4-8 parts of methacrylic acid, E-513-9 parts of epoxy resin, 2-6 parts of coumarone indene resin, different
4-9 parts of cyanate, 3-6 parts of polyphosphate, 3-6 parts of butylene terephthalate, 2-5 parts of hydrogenated styrene, low density polyethylene (LDPE)
1-5 parts, 4-8 parts of nano-ceramic powder, 3-6 parts of nm-class boron nitride, 2-5 parts of zinc borate, 1-5 parts of aluminium triphosphate, nano aluminium oxide
3-6 parts, 2-6 parts of calcium sulfate crystal whiskers, 1-4 parts of chlorinated paraffin, 3-5 parts of micaceous iron oxide, 4-8 parts of pine tar, polyadipate 2-5
Part, 1-5 parts of benzotriazole, 4-6 parts of aluminum diethylphosphinate, 8-10 parts of antimony oxide, 5-8 parts of kodalk, silane are even
Join 2-4 parts of agent KH-560, auxiliary agent 8-16 parts heat resistance modified.
Further, the raw material of the heat resistance modified auxiliary agent includes by weight：5-15 parts of magnesium hydroxide, distilled water 10-
20 parts, 4-8 parts of Silane coupling reagent KH-570,2-6 parts of Vitrified powder, mass percent be 4-6% 1-5 parts of hydrochloric acid solution, methyl
2-6 parts of methyl acrylate, 2-5 parts of butyl acrylate, 1-4 parts of Kynoar, 3-6 parts of benzoyl peroxide, carbamate
2-5 parts, 1-5 parts of isopropyl acrylate, 4-8 parts of organosilicon montmorillonite, 2-6 parts of white carbon, 4-8 parts of wood fibre.
Further, the heat resistance modified auxiliary agent is prepared by following technique：By magnesium hydroxide in 100-120 DEG C of drying
2-6h is subsequently added into distilled water and is uniformly mixed, and is warming up to 40-50 DEG C, keeps the temperature 5-15min, then adds in silane coupling agent KH-
570 are uniformly mixed, and stir 0.5-1.5h in 3500-4500r/min rotating speeds, are filtered after emulsification, in 110-120 DEG C of dry 2-4h,
Material a is obtained after being ground up, sieved；Vitrified powder is put into calcining furnace and calcines 2-5h at 820-920 DEG C, cools down, is put into quality hundred
Fraction is that 1-3h is impregnated in the hydrochloric acid solution of 4-6%, and filtering is taken out, and cleans drying with clear water, crushing obtains material b；By methyl
Methyl acrylate, butyl acrylate, Kynoar and benzoyl peroxide are uniformly mixed, in room temperature ultrasonic disperse 25-
45min obtains material c after dissolving；Then by material a, material b, material c, carbamate, isopropyl acrylate, organosilicon
Montmorillonite, white carbon and wood fibre are uniformly mixed, and are stirred 10-20min in 1500-2500r/min rotating speeds, are then carried out water-bath
It heats and stirs, temperature control is 70-90 DEG C, mixing speed 400-500r/min, then protects lower heat preservation 1-3h in nitrogen,
Heat resistance modified auxiliary agent is obtained after natural cooling.
The present invention also provides a kind of preparation methods of heat-resisting PVC resin, include the following steps：
S1, by weight by Corvic, end hydroxy butadiene, polyphenylene sulfide, methacrylic acid, epoxy resin
E-51 and coumarone indene resin are uniformly mixed, and 10-30min is stirred in 850-1050r/min rotating speeds, are warming up to 80-90 DEG C, heat preservation
Then it is brilliant to add in nano-ceramic powder, nm-class boron nitride, zinc borate, aluminium triphosphate, nano aluminium oxide, calcium sulfate by 20-40min
Palpus, chlorinated paraffin, micaceous iron oxide, pine tar, polyadipate and benzotriazole are uniformly mixed, and ball milling postcooling to room temperature obtains
To base-material；
S2, aluminum diethylphosphinate, antimony oxide, kodalk, heat resistance modified auxiliary agent are uniformly mixed, are warming up to
60-80 DEG C, 10-20min is kept the temperature, silane coupling agent KH-560 is then added in and is uniformly mixed, be continuously heating to 110-120 DEG C, protect
Warm 5-15min is cooled to room temperature to obtain modified materials；
S3, base-material is warming up to 90-110 DEG C, keeps the temperature 15-35min, be subsequently added into modified materials, isocyanates, polyphosphoric acid
Ester, butylene terephthalate, hydrogenated styrene and low density polyethylene (LDPE) are uniformly mixed, and are cooled to 80-90 DEG C, keep the temperature 20-
30min then stirs 1-2h in 1350-1550r/min rotating speeds, is cooled to room temperature to obtain heat-resisting PVC resin.
The invention has the advantages that：(1) by the data of embodiment 1-3 and comparative example 7 as it can be seen that using embodiment 1-
The heat resistance of 3 heat-resisting PVC resins significantly improves；Simultaneously by the data of embodiment 1-3 as it can be seen that embodiment 1 is optimal reality
Apply example.
(2) by embodiment 1 and the data of comparative example 1-6 as it can be seen that aluminum diethylphosphinate, antimony oxide, kodalk,
Silane coupling agent KH-560 and heat resistance modified auxiliary agent add simultaneously plays synergistic effect in heat-resisting PVC resin is prepared,
The heat resistance of heat-resisting PVC resin is significantly improved, this may be：Aluminum diethylphosphinate, antimony oxide, inclined boron
Sour sodium, silane coupling agent KH-560 and heat resistance modified auxiliary agent are applied to as modified system in the preparation of Corvic, profit
Acted on the graft modification of silane coupling agent KH-560, realize aluminum diethylphosphinate, antimony oxide, kodalk and
The base-material of the hydroxyl on heat resistance modified auxiliary agent surface and Corvic, which is realized, to be grafted, and imparts excellent resistance to of Corvic
Hot property, while the resistance to thermal enhancement of heat resistance modified auxiliary agent is make use of, wherein heat resistance modified auxiliary agent is by the way that magnesium hydroxide is done
It is dry, it is subsequently added into distilled water and is uniformly mixed, heat up, then heat preservation adds in Silane coupling reagent KH-570 and is uniformly mixed, stirs, breast
It is filtered after change, it is dry, material a is obtained after being ground up, sieved；Vitrified powder is put into calcining furnace and is calcined, cools down, is put into hydrochloric acid solution
Middle immersion, filtering are taken out, and clean drying with clear water, crushing obtains material b；By methyl methacrylate, butyl acrylate, gather partially
Vinyl fluoride and benzoyl peroxide are uniformly mixed, and material c is obtained after room temperature ultrasonic disperse, dissolving；Then by material a, material
B, material c, carbamate, isopropyl acrylate, organosilicon montmorillonite, white carbon and wood fibre are uniformly mixed, and stirring connects
It carry out heating water bath and stirs, then protect lower heat preservation in nitrogen, obtain heat resistance modified auxiliary agent after natural cooling, apply to this
In the preparation of invention Corvic, under the action of silane coupling agent KH-560, the master with Corvic is realized
Material carries out grafting combination, effectively increases the heat resistance of Corvic.
Specific embodiment
The present invention is described in detail with reference to specific embodiment, it should be appreciated that embodiment is served only for illustrating this hair
Bright rather than for limiting the invention, any modification made on the basis of the present invention, equivalent substitution etc. are in this hair
In bright protection domain.
In embodiment, the heat-resisting PVC resin, in units of parts by weight, including following raw material：Polyvinyl chloride
40-50 parts of resin, 15-25 parts of end hydroxy butadiene, 5-15 parts of polyphenylene sulfide, 4-8 parts of methacrylic acid, epoxy resin E-51
3-9 parts, 2-6 parts of coumarone indene resin, 4-9 parts of isocyanates, 3-6 parts of polyphosphate, 3-6 parts of butylene terephthalate, hydrogenation
2-5 parts of styrene, 1-5 parts of low density polyethylene (LDPE), 4-8 parts of nano-ceramic powder, 3-6 parts of nm-class boron nitride, 2-5 parts of zinc borate, three
1-5 parts of poly aluminium phosphate, 3-6 parts of nano aluminium oxide, 2-6 parts of calcium sulfate crystal whiskers, 1-4 parts of chlorinated paraffin, 3-5 parts of micaceous iron oxide,
4-8 parts of pine tar, 2-5 parts of polyadipate, 1-5 parts of benzotriazole, 4-6 parts of aluminum diethylphosphinate, antimony oxide 8-10
It is part, 5-8 parts of kodalk, 2-4 parts of silane coupling agent KH-560, auxiliary agent 8-16 parts heat resistance modified.
The heat resistance modified auxiliary agent is prepared by following technique：By weight by 5-15 parts of magnesium hydroxides in 100-120
DEG C dry 2-6h, is subsequently added into 10-20 part distilled water and is uniformly mixed, be warming up to 40-50 DEG C, then heat preservation 5-15min adds in 4-
8 parts of Silane coupling reagent KH-570s are uniformly mixed, and are stirred 0.5-1.5h in 3500-4500r/min rotating speeds, are filtered after emulsification, in
110-120 DEG C of dry 2-4h, obtains material a after being ground up, sieved；2-6 parts of Vitrified powders are put into calcining furnace at 820-920 DEG C
2-5h is calcined, cooling is put into the hydrochloric acid solution that 1-5 parts of mass percents are 4-6% and impregnates 1-3h, and filtering is taken out, and uses clear water
Drying is cleaned, crushing obtains material b；By 2-6 parts of methyl methacrylates, 2-5 parts of butyl acrylates, 1-4 parts of Kynoar
It is uniformly mixed with 3-6 parts of benzoyl peroxides, in room temperature ultrasonic disperse 25-45min, material c is obtained after dissolving；Then by material
A, material b, c, 2-5 parts of carbamates of material, 1-5 parts of isopropyl acrylates, 4-8 parts of organosilicon montmorillonites, 2-6 parts of white carbons
It is uniformly mixed with 4-8 parts of wood fibres, 10-20min is stirred in 1500-2500r/min rotating speeds, then carried out heating water bath and stir
It mixes, temperature control is 70-90 DEG C, mixing speed 400-500r/min, then protects lower heat preservation 1-3h, natural cooling in nitrogen
After obtain heat resistance modified auxiliary agent.
The preparation method of the heat-resisting PVC resin, comprises the following steps：
S1, by weight by Corvic, end hydroxy butadiene, polyphenylene sulfide, methacrylic acid, epoxy resin
E-51 and coumarone indene resin are uniformly mixed, and 10-30min is stirred in 850-1050r/min rotating speeds, are warming up to 80-90 DEG C, heat preservation
Then it is brilliant to add in nano-ceramic powder, nm-class boron nitride, zinc borate, aluminium triphosphate, nano aluminium oxide, calcium sulfate by 20-40min
Palpus, chlorinated paraffin, micaceous iron oxide, pine tar, polyadipate and benzotriazole are uniformly mixed, and ball milling postcooling to room temperature obtains
To base-material；
S2, aluminum diethylphosphinate, antimony oxide, kodalk, heat resistance modified auxiliary agent are uniformly mixed, are warming up to
60-80 DEG C, 10-20min is kept the temperature, silane coupling agent KH-560 is then added in and is uniformly mixed, be continuously heating to 110-120 DEG C, protect
Warm 5-15min is cooled to room temperature to obtain modified materials；
S3, base-material is warming up to 90-110 DEG C, keeps the temperature 15-35min, be subsequently added into modified materials, isocyanates, polyphosphoric acid
Ester, butylene terephthalate, hydrogenated styrene and low density polyethylene (LDPE) are uniformly mixed, and are cooled to 80-90 DEG C, keep the temperature 20-
30min then stirs 1-2h in 1350-1550r/min rotating speeds, is cooled to room temperature to obtain heat-resisting PVC resin.
Below by more specific embodiment, the present invention will be described.
Embodiment 1
A kind of heat-resisting PVC resin, in units of parts by weight, including following raw material：45 parts of Corvic, end
It is 20 parts of hydroxyl polybutadiene, 10 parts of polyphenylene sulfide, 6 parts of methacrylic acid, E-516 parts of epoxy resin, 4 parts of coumarone indene resin, different
6.5 parts of cyanate, 4.5 parts of polyphosphate, 4.5 parts of butylene terephthalate, 3 parts of hydrogenated styrene, low density polyethylene (LDPE) 3
Part, 6 parts of nano-ceramic powder, 4.5 parts of nm-class boron nitride, 4 parts of zinc borate, 3 parts of aluminium triphosphate, 4 parts of nano aluminium oxide, calcium sulfate
4 parts of whisker, 3 parts of chlorinated paraffin, 4 parts of micaceous iron oxide, 6 parts of pine tar, 3.5 parts of polyadipate, 3 parts of benzotriazole, diethyl
5 parts of base phosphinic acids aluminium, 9 parts of antimony oxide, 6 parts of kodalk, KH-5603 parts of silane coupling agent, 12 parts of heat resistance modified auxiliary agent.
The heat resistance modified auxiliary agent is prepared by following technique：By weight by 10 parts of magnesium hydroxides in 110 DEG C of dryings
4h is subsequently added into 15 parts of distilled water and is uniformly mixed, and is warming up to 45 DEG C, keeps the temperature 10min, then adds in 6 parts of silane coupling agent KH-
570 are uniformly mixed, and stir 1h in 4000r/min rotating speeds, are filtered after emulsification, in 115 DEG C of dry 3h, material is obtained after being ground up, sieved
a；4 parts of Vitrified powders are put into calcining furnace and calcine 3.5h at 870 DEG C, are cooled down, are put into the hydrochloric acid that 3 parts of mass percents are 5%
2h is impregnated in solution, filtering is taken out, and cleans drying with clear water, crushing obtains material b；By 4 parts of methyl methacrylates, 3.5 parts
Butyl acrylate, 3 parts of Kynoar and 4.5 parts of benzoyl peroxides are uniformly mixed, in room temperature ultrasonic disperse 35min, dissolving
After obtain material c；Then by material a, material b, material c, 3.5 parts of carbamates, 3 parts of isopropyl acrylates, 6 parts of organosilicons
Montmorillonite, 4 parts of white carbons and 6 parts of wood fibres are uniformly mixed, and 15min is stirred in 2000r/min rotating speeds, are then carried out water-bath and are added
Heat simultaneously stirs, and temperature control is 80 DEG C, mixing speed 450r/min, then the heat preservation 2h under nitrogen is protected, after natural cooling
Obtain heat resistance modified auxiliary agent.
The preparation method of the heat-resisting PVC resin, comprises the following steps：
S1, by weight by Corvic, end hydroxy butadiene, polyphenylene sulfide, methacrylic acid, epoxy resin
E-51 and coumarone indene resin are uniformly mixed, and are stirred 20min in 950r/min rotating speeds, are warming up to 85 DEG C, keep the temperature 30min, Ran Houjia
Enter nano-ceramic powder, nm-class boron nitride, zinc borate, aluminium triphosphate, nano aluminium oxide, calcium sulfate crystal whiskers, chlorinated paraffin, mica
Iron oxide, pine tar, polyadipate and benzotriazole are uniformly mixed, and ball milling postcooling to room temperature obtains base-material；
S2, aluminum diethylphosphinate, antimony oxide, kodalk, heat resistance modified auxiliary agent are uniformly mixed, are warming up to 70
DEG C, 15min is kept the temperature, silane coupling agent KH-560 is then added in and is uniformly mixed, be continuously heating to 115 DEG C, keeps the temperature 10min, cooling
Modified materials are obtained to room temperature；
S3, base-material is warming up to 100 DEG C, keeps the temperature 25min, be subsequently added into modified materials, isocyanates, polyphosphate, to benzene
Dioctyl phthalate fourth diester, hydrogenated styrene and low density polyethylene (LDPE) are uniformly mixed, and are cooled to 85 DEG C, keep the temperature 25min, then in
1450r/min rotating speeds stir 1.5h, are cooled to room temperature to obtain heat-resisting PVC resin.
Embodiment 2
A kind of heat-resisting PVC resin, in units of parts by weight, including following raw material：40 parts of Corvic, end
25 parts of hydroxyl polybutadiene, 5 parts of polyphenylene sulfide, 8 parts of methacrylic acid, E-513 parts of epoxy resin, 6 parts of coumarone indene resin, isocyanide
4 parts of acid esters, 6 parts of polyphosphate, 3 parts of butylene terephthalate, 5 parts of hydrogenated styrene, low density polyethylene (LDPE) 1 part, nanometer pottery
8 parts of porcelain powder, 3 parts of nm-class boron nitride, 5 parts of zinc borate, 1 part of aluminium triphosphate, 6 parts of nano aluminium oxide, 2 parts of calcium sulfate crystal whiskers, chlorine
4 parts of fossil waxes, 3 parts of micaceous iron oxide, 8 parts of pine tar, 2 parts of polyadipate, 5 parts of benzotriazole, aluminum diethylphosphinate 4
Part, 10 parts of antimony oxide, 5 parts of kodalk, 4 parts of silane coupling agent KH-560,8 parts of heat resistance modified auxiliary agent.
The heat resistance modified auxiliary agent is prepared by following technique：By weight by 5 parts of magnesium hydroxides in 120 DEG C of dryings
2h is subsequently added into 20 parts of distilled water and is uniformly mixed, and is warming up to 40 DEG C, keeps the temperature 15min, then adds in 4 parts of silane coupling agent KH-
570 are uniformly mixed, and stir 0.5h in 4500r/min rotating speeds, are filtered after emulsification, in 120 DEG C of dry 2h, object is obtained after being ground up, sieved
Expect a；6 parts of Vitrified powders are put into calcining furnace and calcine 5h at 820 DEG C, are cooled down, are put into the hydrochloric acid that 1 part of mass percent is 6%
1h is impregnated in solution, filtering is taken out, and cleans drying with clear water, crushing obtains material b；By 6 parts of methyl methacrylates, 2 part third
Olefin(e) acid butyl ester, 4 parts of Kynoar and 3 parts of benzoyl peroxides are uniformly mixed, and in room temperature ultrasonic disperse 45min, are obtained after dissolving
To material c；Then material a, material b, material c, 2 parts of carbamates, 5 parts of isopropyl acrylates, 4 parts of organosilicons are covered de-
Soil, 6 parts of white carbons and 4 parts of wood fibres are uniformly mixed, and are stirred 10min in 2500r/min rotating speeds, are then carried out heating water bath simultaneously
Stirring, temperature control are 90 DEG C, mixing speed 400r/min, then protect lower heat preservation 3h in nitrogen, are obtained after natural cooling
Heat resistance modified auxiliary agent.
The preparation method of the heat-resisting PVC resin, comprises the following steps：
S1, by weight by Corvic, end hydroxy butadiene, polyphenylene sulfide, methacrylic acid, epoxy resin
E-51 and coumarone indene resin are uniformly mixed, and are stirred 30min in 850r/min rotating speeds, are warming up to 80 DEG C, keep the temperature 40min, Ran Houjia
Enter nano-ceramic powder, nm-class boron nitride, zinc borate, aluminium triphosphate, nano aluminium oxide, calcium sulfate crystal whiskers, chlorinated paraffin, mica
Iron oxide, pine tar, polyadipate and benzotriazole are uniformly mixed, and ball milling postcooling to room temperature obtains base-material；
S2, aluminum diethylphosphinate, antimony oxide, kodalk, heat resistance modified auxiliary agent are uniformly mixed, are warming up to 60
DEG C, 20min is kept the temperature, silane coupling agent KH-560 is then added in and is uniformly mixed, be continuously heating to 110 DEG C, keeps the temperature 15min, cooling
Modified materials are obtained to room temperature；
S3, base-material is warming up to 90 DEG C, keeps the temperature 35min, be subsequently added into modified materials, isocyanates, polyphosphate, to benzene two
Formic acid fourth diester, hydrogenated styrene and low density polyethylene (LDPE) are uniformly mixed, and are cooled to 80 DEG C, 30min are kept the temperature, then in 1350r/
Min rotating speeds stir 2h, are cooled to room temperature to obtain heat-resisting PVC resin.
Embodiment 3
A kind of heat-resisting PVC resin, in units of parts by weight, including following raw material：50 parts of Corvic, end
It is 15 parts of hydroxyl polybutadiene, 15 parts of polyphenylene sulfide, 4 parts of methacrylic acid, E-519 parts of epoxy resin, 2 parts of coumarone indene resin, different
9 parts of cyanate, 3 parts of polyphosphate, 6 parts of butylene terephthalate, 2 parts of hydrogenated styrene, low density polyethylene (LDPE) 5 part, nanometer
4 parts of ceramic powder, 6 parts of nm-class boron nitride, 2 parts of zinc borate, 5 parts of aluminium triphosphate, 3 parts of nano aluminium oxide, 6 parts of calcium sulfate crystal whiskers,
1 part of chlorinated paraffin, 5 parts of micaceous iron oxide, 4 parts of pine tar, 5 parts of polyadipate, 1 part of benzotriazole, aluminum diethylphosphinate 6
Part, 8 parts of antimony oxide, 8 parts of kodalk, 2 parts of silane coupling agent KH-560,16 parts of heat resistance modified auxiliary agent.
The heat resistance modified auxiliary agent is prepared by following technique：By weight by 15 parts of magnesium hydroxides in 100 DEG C of dryings
6h is subsequently added into 10 parts of distilled water and is uniformly mixed, and is warming up to 50 DEG C, keeps the temperature 5min, then adds in 8 parts of Silane coupling reagent KH-570s
It is uniformly mixed, stirs 1.5h in 3500r/min rotating speeds, filtered after emulsification, in 110 DEG C of dry 4h, material is obtained after being ground up, sieved
a；2 parts of Vitrified powders are put into calcining furnace and calcine 2h at 920 DEG C, are cooled down, it is molten to be put into the hydrochloric acid that 5 parts of mass percents are 4%
3h is impregnated in liquid, filtering is taken out, and cleans drying with clear water, crushing obtains material b；By 2 parts of methyl methacrylates, 5 parts of propylene
Acid butyl ester, 1 part of Kynoar and 6 parts of benzoyl peroxides are uniformly mixed, and in room temperature ultrasonic disperse 25min, are obtained after dissolving
Material c；Then by material a, material b, material c, 5 parts of carbamates, 1 part of isopropyl acrylate, 8 parts of organosilicon montmorillonites, 2
Part white carbon and 8 parts of wood fibres are uniformly mixed, and 20min is stirred in 1500r/min rotating speeds, are then carried out heating water bath and are stirred
It mixes, temperature control is 70 DEG C, mixing speed 500r/min, then protects lower heat preservation 1h in nitrogen, is obtained after natural cooling resistance to
Heat modification auxiliary agent.
The preparation method of the heat-resisting PVC resin, comprises the following steps：
S1, by weight by Corvic, end hydroxy butadiene, polyphenylene sulfide, methacrylic acid, epoxy resin
E-51 and coumarone indene resin are uniformly mixed, and are stirred 10min in 1050r/min rotating speeds, are warming up to 90 DEG C, keep the temperature 20min, Ran Houjia
Enter nano-ceramic powder, nm-class boron nitride, zinc borate, aluminium triphosphate, nano aluminium oxide, calcium sulfate crystal whiskers, chlorinated paraffin, mica
Iron oxide, pine tar, polyadipate and benzotriazole are uniformly mixed, and ball milling postcooling to room temperature obtains base-material；
S2, aluminum diethylphosphinate, antimony oxide, kodalk, heat resistance modified auxiliary agent are uniformly mixed, are warming up to 80
DEG C, 10min is kept the temperature, silane coupling agent KH-560 is then added in and is uniformly mixed, be continuously heating to 120 DEG C, keep the temperature 5min, be cooled to
Room temperature obtains modified materials；
S3, base-material is warming up to 110 DEG C, keeps the temperature 15min, be subsequently added into modified materials, isocyanates, polyphosphate, to benzene
Dioctyl phthalate fourth diester, hydrogenated styrene and low density polyethylene (LDPE) are uniformly mixed, and are cooled to 90 DEG C, keep the temperature 20min, then in
1550r/min rotating speeds stir 1h, are cooled to room temperature to obtain heat-resisting PVC resin.
Comparative example 1
It is essentially identical with the preparation process of embodiment 1, have only unlike prepare in the raw material of heat-resisting PVC resin
Lack aluminum diethylphosphinate, antimony oxide, kodalk, silane coupling agent KH-560, heat resistance modified auxiliary agent.
Comparative example 2
It is essentially identical with the preparation process of embodiment 1, have only unlike prepare in the raw material of heat-resisting PVC resin
Lack aluminum diethylphosphinate.
Comparative example 3
It is essentially identical with the preparation process of embodiment 1, have only unlike prepare in the raw material of heat-resisting PVC resin
Lack antimony oxide.
Comparative example 4
It is essentially identical with the preparation process of embodiment 1, have only unlike prepare in the raw material of heat-resisting PVC resin
Lack kodalk.
Comparative example 5
It is essentially identical with the preparation process of embodiment 1, have only unlike prepare in the raw material of heat-resisting PVC resin
Lack silane coupling agent KH-560.
Comparative example 6
It is essentially identical with the preparation process of embodiment 1, have only unlike prepare in the raw material of heat-resisting PVC resin
Lack heat resistance modified auxiliary agent.
Comparative example 7
Using a kind of Chinese patent application document " Corvic and its preparation method and application (application publication number：
CN101143954A) " technique of embodiment prepares Corvic.
The Corvic for measuring embodiment 1-3 and comparative example 1-7 carries out indices detection, obtained testing result
Such as following table：
| Experimental project | Duration of fire resistance (s) |
| Embodiment 1 | 16.8 |
| Embodiment 2 | 15.1 |
| Embodiment 3 | 2.8 |
| Comparative example 1 | 13.6 |
| Comparative example 2 | 14.9 |
| Comparative example 3 | 15.7 |
| Comparative example 4 | 15.2 |
| Comparative example 5 | 16.1 |
| Comparative example 6 | 15.9 |
| Comparative example 7 | 1.8-2.4 |
(1) by the data of embodiment 1-3 and comparative example 7 as it can be seen that using the heat-resisting of embodiment 1-3 heat-resisting PVC resins
Performance significantly improves；Simultaneously by the data of embodiment 1-3 as it can be seen that embodiment 1 is optimum embodiment.
(2) by embodiment 1 and the data of comparative example 1-6 as it can be seen that aluminum diethylphosphinate, antimony oxide, kodalk,
Silane coupling agent KH-560 and heat resistance modified auxiliary agent add simultaneously plays synergistic effect in heat-resisting PVC resin is prepared,
The heat resistance of heat-resisting PVC resin is significantly improved, this may be：Aluminum diethylphosphinate, antimony oxide, inclined boron
Sour sodium, silane coupling agent KH-560 and heat resistance modified auxiliary agent are applied to as modified system in the preparation of Corvic, profit
Acted on the graft modification of silane coupling agent KH-560, realize aluminum diethylphosphinate, antimony oxide, kodalk and
The base-material of the hydroxyl on heat resistance modified auxiliary agent surface and Corvic, which is realized, to be grafted, and imparts excellent resistance to of Corvic
Hot property, while the resistance to thermal enhancement of heat resistance modified auxiliary agent is make use of, wherein heat resistance modified auxiliary agent is by the way that magnesium hydroxide is done
It is dry, it is subsequently added into distilled water and is uniformly mixed, heat up, then heat preservation adds in Silane coupling reagent KH-570 and is uniformly mixed, stirs, breast
It is filtered after change, it is dry, material a is obtained after being ground up, sieved；Vitrified powder is put into calcining furnace and is calcined, cools down, is put into hydrochloric acid solution
Middle immersion, filtering are taken out, and clean drying with clear water, crushing obtains material b；By methyl methacrylate, butyl acrylate, gather partially
Vinyl fluoride and benzoyl peroxide are uniformly mixed, and material c is obtained after room temperature ultrasonic disperse, dissolving；Then by material a, material
B, material c, carbamate, isopropyl acrylate, organosilicon montmorillonite, white carbon and wood fibre are uniformly mixed, and stirring connects
It carry out heating water bath and stirs, then protect lower heat preservation in nitrogen, obtain heat resistance modified auxiliary agent after natural cooling, apply to this
In the preparation of invention Corvic, under the action of silane coupling agent KH-560, the master with Corvic is realized
Material carries out grafting combination, effectively increases the heat resistance of Corvic.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, technique according to the invention scheme and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (6)
1. a kind of heat-resisting PVC resin, which is characterized in that including following raw material：Corvic, terminal hydroxy group polybutadiene
Alkene, polyphenylene sulfide, methacrylic acid, epoxy resin E-51, coumarone indene resin, isocyanates, polyphosphate, terephthalic acid (TPA) fourth
It is diester, hydrogenated styrene, low density polyethylene (LDPE), nano-ceramic powder, nm-class boron nitride, zinc borate, aluminium triphosphate, nano oxidized
Aluminium, calcium sulfate crystal whiskers, chlorinated paraffin, micaceous iron oxide, pine tar, polyadipate, benzotriazole, aluminum diethylphosphinate,
Antimony oxide, kodalk, silane coupling agent KH-560, heat resistance modified auxiliary agent；
The aluminum diethylphosphinate, antimony oxide, kodalk, silane coupling agent KH-560, the weight of heat resistance modified auxiliary agent
Amount is than being (4-6)：(8-10)：(5-8)：(2-4)：(8-16).
2. heat-resisting PVC resin according to claim 1, which is characterized in that the aluminum diethylphosphinate, three oxygen
It is 5 to change two antimony, kodalk, silane coupling agent KH-560, the weight ratio of heat resistance modified auxiliary agent：9：6.5：3：12.
3. heat-resisting PVC resin according to claim 1 or 2, which is characterized in that in units of parts by weight, including with
Lower raw material：40-50 parts of Corvic, 15-25 parts of end hydroxy butadiene, 5-15 parts of polyphenylene sulfide, methacrylic acid 4-8
Part, 3-9 parts of epoxy resin E-51,2-6 parts of coumarone indene resin, 4-9 parts of isocyanates, 3-6 parts of polyphosphate, terephthalic acid (TPA)
3-6 parts of fourth diester, 2-5 parts of hydrogenated styrene, 1-5 parts of low density polyethylene (LDPE), 4-8 parts of nano-ceramic powder, nm-class boron nitride 3-6
Part, 2-5 parts of zinc borate, 1-5 parts of aluminium triphosphate, 3-6 parts of nano aluminium oxide, 2-6 parts of calcium sulfate crystal whiskers, 1-4 parts of chlorinated paraffin,
3-5 parts of micaceous iron oxide, 4-8 parts of pine tar, 2-5 parts of polyadipate, 1-5 parts of benzotriazole, aluminum diethylphosphinate 4-6
It is part, 8-10 parts of antimony oxide, 5-8 parts of kodalk, 2-4 parts of silane coupling agent KH-560, auxiliary agent 8-16 parts heat resistance modified.
4. according to claim 1-3 any one of them heat-resisting PVC resins, which is characterized in that the heat resistance modified auxiliary agent
Raw material include by weight：5-15 parts of magnesium hydroxide, 10-20 parts of distilled water, 4-8 parts of Silane coupling reagent KH-570, Vitrified powder
2-6 parts, mass percent be 4-6% 2-5 parts of 2-6 parts of 1-5 part of hydrochloric acid solution, methyl methacrylate, butyl acrylate, gather
1-4 parts of vinylidene, 3-6 parts of benzoyl peroxide, 2-5 parts of carbamate, 1-5 parts of isopropyl acrylate, organosilicon cover de-
4-8 parts native, 2-6 parts of white carbon, 4-8 parts of wood fibre.
5. according to claim 1-4 any one of them heat-resisting PVC resins, which is characterized in that the heat resistance modified auxiliary agent
It is prepared by following technique：By magnesium hydroxide in 100-120 DEG C of dry 2-6h, it is subsequently added into distilled water and is uniformly mixed, heat up
To 40-50 DEG C, 5-15min is kept the temperature, Silane coupling reagent KH-570 is then added in and is uniformly mixed, stirred in 3500-4500r/min rotating speeds
0.5-1.5h is mixed, is filtered after emulsification, in 110-120 DEG C of dry 2-4h, material a is obtained after being ground up, sieved；Vitrified powder is put into and is forged
It burns in stove and 2-5h is calcined at 820-920 DEG C, cool down, be put into the hydrochloric acid solution that mass percent is 4-6% and impregnate 1-3h, mistake
Leaching goes out, and cleans drying with clear water, crushing obtains material b；By methyl methacrylate, butyl acrylate, Kynoar and
Benzoyl peroxide is uniformly mixed, and in room temperature ultrasonic disperse 25-45min, material c is obtained after dissolving；Then by material a, material
B, material c, carbamate, isopropyl acrylate, organosilicon montmorillonite, white carbon and wood fibre are uniformly mixed, in 1500-
2500r/min rotating speeds stir 10-20min, then carry out heating water bath and stir, and temperature control is 70-90 DEG C, and mixing speed is
Then 400-500r/min protects lower heat preservation 1-3h in nitrogen, heat resistance modified auxiliary agent is obtained after natural cooling.
A kind of 6. preparation method according to claim 1-5 any one of them heat-resisting PVC resins, which is characterized in that bag
Include following steps：
S1, by weight by Corvic, end hydroxy butadiene, polyphenylene sulfide, methacrylic acid, epoxy resin E-51
It is uniformly mixed with coumarone indene resin, stirs 10-30min in 850-1050r/min rotating speeds, be warming up to 80-90 DEG C, keep the temperature 20-
40min, then add in nano-ceramic powder, nm-class boron nitride, zinc borate, aluminium triphosphate, nano aluminium oxide, calcium sulfate crystal whiskers,
Chlorinated paraffin, micaceous iron oxide, pine tar, polyadipate and benzotriazole are uniformly mixed, and ball milling postcooling to room temperature obtains
Base-material；
S2, aluminum diethylphosphinate, antimony oxide, kodalk, heat resistance modified auxiliary agent are uniformly mixed, are warming up to 60-80
DEG C, 10-20min is kept the temperature, silane coupling agent KH-560 is then added in and is uniformly mixed, be continuously heating to 110-120 DEG C, keep the temperature 5-
15min is cooled to room temperature to obtain modified materials；
S3, base-material is warming up to 90-110 DEG C, keeps the temperature 15-35min, be subsequently added into modified materials, isocyanates, polyphosphate, right
Terephtha-late, hydrogenated styrene and low density polyethylene (LDPE) are uniformly mixed, and are cooled to 80-90 DEG C, are kept the temperature 20-30min, are connect
It and stirs 1-2h in 1350-1550r/min rotating speeds, be cooled to room temperature to obtain heat-resisting PVC resin.
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| CN108864897A (en) * | 2018-06-20 | 2018-11-23 | 天长市金陵电子有限责任公司 | A kind of electrostatic spraying Corrosion-resistant heat-resistant paint and preparation method thereof |
| CN110483916A (en) * | 2019-08-26 | 2019-11-22 | 安徽华塑股份有限公司 | A kind of heat-resistant polyvinyl chloride composite material |
| CN113861594A (en) * | 2021-11-19 | 2021-12-31 | 广东冠盛新材料股份有限公司 | Flame-retardant high-temperature-resistant PVC (polyvinyl chloride) film for graphene electrothermal film and preparation method thereof |
| CN116693989A (en) * | 2023-08-09 | 2023-09-05 | 潍坊潍星联合橡塑有限公司 | Corrosion-resistant cable outer sheath material |
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| CN103540053A (en) * | 2013-09-18 | 2014-01-29 | 天长市富达电子有限公司 | Heat and flame resistant polyvinyl chloride power cord sheath material and preparation method thereof |
| CN104004292A (en) * | 2014-04-22 | 2014-08-27 | 天长市富信电子有限公司 | Heat resistant polyvinyl chloride sheath material for refrigerator and preparation method thereof |
| CN107312332A (en) * | 2017-06-19 | 2017-11-03 | 合肥斯科尔智能科技有限公司 | A kind of 3D printing material of architectural engineering high tenacity high temperature oxidation resisting |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103540053A (en) * | 2013-09-18 | 2014-01-29 | 天长市富达电子有限公司 | Heat and flame resistant polyvinyl chloride power cord sheath material and preparation method thereof |
| CN104004292A (en) * | 2014-04-22 | 2014-08-27 | 天长市富信电子有限公司 | Heat resistant polyvinyl chloride sheath material for refrigerator and preparation method thereof |
| CN107312332A (en) * | 2017-06-19 | 2017-11-03 | 合肥斯科尔智能科技有限公司 | A kind of 3D printing material of architectural engineering high tenacity high temperature oxidation resisting |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108864897A (en) * | 2018-06-20 | 2018-11-23 | 天长市金陵电子有限责任公司 | A kind of electrostatic spraying Corrosion-resistant heat-resistant paint and preparation method thereof |
| CN110483916A (en) * | 2019-08-26 | 2019-11-22 | 安徽华塑股份有限公司 | A kind of heat-resistant polyvinyl chloride composite material |
| CN113861594A (en) * | 2021-11-19 | 2021-12-31 | 广东冠盛新材料股份有限公司 | Flame-retardant high-temperature-resistant PVC (polyvinyl chloride) film for graphene electrothermal film and preparation method thereof |
| CN116693989A (en) * | 2023-08-09 | 2023-09-05 | 潍坊潍星联合橡塑有限公司 | Corrosion-resistant cable outer sheath material |
| CN116693989B (en) * | 2023-08-09 | 2023-09-29 | 潍坊潍星联合橡塑有限公司 | Corrosion-resistant cable outer sheath material |
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