CN108456388A - A kind of filling-modified PVC of calcium sulfide and preparation method thereof - Google Patents
A kind of filling-modified PVC of calcium sulfide and preparation method thereof Download PDFInfo
- Publication number
- CN108456388A CN108456388A CN201810158055.3A CN201810158055A CN108456388A CN 108456388 A CN108456388 A CN 108456388A CN 201810158055 A CN201810158055 A CN 201810158055A CN 108456388 A CN108456388 A CN 108456388A
- Authority
- CN
- China
- Prior art keywords
- parts
- modified
- ethyl alcohol
- calcium
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C08L27/22—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 modified by chemical after-treatment
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- 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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3009—Sulfides
- C08K2003/3018—Sulfides of magnesium, calcium, strontium or barium
-
- 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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Developing Agents For Electrophotography (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention is related to a kind of modified PVC, including following raw material components：Epoxychloropropane modified PVC, modified calcium sulfide, aluminium oxide, modified calcium sulfate and 1,3,5 trimethyls 2,4,6（3,5 di-t-butyl, 4 hydroxyphenylmethyl）Benzene, epoxychloropropane modified PVC pellets, which are reacted by PVC pellets, epoxychloropropane, sodium hydroxide, ethyl alcohol, water and diethylin for methyltriethoxysilane, to be made, modified calcium sulfide is by mono phosphoric acid ester ethyl ester, 1,5 naphthylenediamines, ethyl alcohol and calcium sulfide reaction are made, calcium sulfide, which is reacted by calcium sulfhydrate, water, ethyl alcohol, neopelex, diethylin for methyltriethoxysilane and thiocarbamide, to be made, and modified calcium sulfate is reacted by calcium sulfate, ethyl alcohol, polyvinyl alcohol and polyamide to be made.The invention has the advantages such as excellent ultraviolet-shielding type, anti-flammability, heat-resisting quantity, mechanical property, heat conductivility, low volume shrinking percentage.
Description
Technical field
The invention is related to a kind of modified PVC and preparation method thereof.
Background technology
Polyvinyl chloride have it is light, chemical resistance is excellent, and flow resistance is small, and mechanical strength is big, electric insulating quality
It is good, the advantages such as water quality are not influenced.Polyvinyl chloride can be used and the methods of squeeze out, injects, molds, is blow molded molding, be widely used in manufacturing
Plastic shoes, artificial leather raincoat, the tablecloth, curtain, cable, handbag, soap box, comb, washing board, writing case, various tubing etc..
Currently, PVC material UV resistant, anti-flammability, heat resistance, mechanical property, filler dispersibility, filler compatibility,
The performances such as heat conductivility need further to be promoted.The invention uses modified calcium sulfate, is modified calcium sulfide, is epoxychloropropane modified
PVC pellets, aluminium oxide are prepared for modified PVC, and various plastic products are prepared by techniques such as extrusion, injection molding, molding, blowings,
This method prepare modifying character for PVC material have excellent UV resistant, anti-flammability, heat resistance, mechanical property, filler dispersibility,
The performances such as filler compatibility, heat conductivility, low volume shrinking percentage.
Invention content
The invention is designed to provide a kind of preparation method of modified PVC, this method by change reactant feed and
The material of technology mode, preparation has excellent UV resistant, anti-flammability, heat resistance, mechanical property, filler dispersibility, filler
The performances such as compatibility, heat conductivility, low volume shrinking percentage.
To achieve the goals above, the technical solution of the invention is as follows.
A kind of modified PVC and preparation method thereof, specifically includes following steps：(1), by calcium sulfate, ethyl alcohol, polyvinyl alcohol and
Polyamide is 100 according to quality parts ratio：30~35：10~15：8~13 are added in reactor, mixing speed 70
~80r/min reacts 1~3h under the conditions of 80~100 DEG C of maintenance system temperature, and at 90 DEG C, -0.07MPa is evaporated under reduced pressure 2h, and 120
DEG C dry 2h, obtains modified calcium sulfate；(2), by calcium sulfhydrate, water, ethyl alcohol, neopelex, diethylin for first
Ethyl triethoxy silicane alkane and thiocarbamide are according to quality parts ratio 100：70~100：150~200：10~20：7~13：30~50 add
Enter into reaction kettle, mixing speed is 120~150r/min, and 2~4h, warp are reacted under the conditions of 40~60 DEG C of maintenance system temperature
Filtering, 1L water washings 3 times, 500mL ethyl alcohol wash 2 times, and under nitrogen protection, 300 DEG C of roasting 3h obtain calcium sulfide；(3), will
Mono phosphoric acid ester ethyl ester, 1,5- naphthylenediamines, ethyl alcohol and calcium sulfide are according to quality parts ratio 100：78~96：100~120：25~30
Be added in reaction kettle, in 135~150 DEG C of temperature, under the conditions of mixing speed is 50~70r/min 1~3 h of reaction to get to
Modified calcium sulfide；(4), by PVC pellets, epoxychloropropane, sodium hydroxide, ethyl alcohol, water and diethylin for methyl triethoxy
Silane is according to quality parts ratio 100：15~20：3~7：15~20：3~5：2~5 are added in open mill, with open mill in temperature
140~190 DEG C of 0.5~2h of hybrid reaction are spent, with extruder in 140~190 DEG C of extruding pelletizations of temperature to get to epoxychloropropane
Modified PVC pellet；(5), by epoxychloropropane modified PVC, modified calcium sulfide, aluminium oxide, modified calcium sulfate and 1,3,5- front threes
Base -2,4,6-（3,5- di-t-butyl -4- hydroxyphenylmethyls）Benzene is according to quality parts ratio 100：4~7：7~12：6~14：1~2
It is added in open mill, with open mill in 140~190 DEG C of 0.5~2h of hybrid reaction of temperature, with extruder in temperature 140~190
DEG C by modified PVC extruding pelletization to get to modified PVC pellet.
The preparation method of modified PVC described in the invention, includes the following steps：
(1), it is 100 according to quality parts ratio by calcium sulfate, ethyl alcohol, polyvinyl alcohol and polyamide：30~35：10~15：8
~13 are added in reactor, and mixing speed is 70~80r/min, and reaction 1 under the conditions of 80~100 DEG C of maintenance system temperature~
3h, at 90 DEG C, -0.07MPa is evaporated under reduced pressure 2h, 120 DEG C of dry 2h, obtains modified calcium sulfate；The polyvinyl alcohol and polyamides
The purpose of polyimide resin is in order to improve the chemical reactivity on calcium sulfate surface.
(2), by calcium sulfhydrate, water, ethyl alcohol, neopelex, diethylin for methyltriethoxysilane and
Thiocarbamide is according to quality parts ratio 100：70~100：150~200：10~20：7~13：30~50 are added in reaction kettle, stirring
Speed is 120~150r/min, and 2~4h is reacted under the conditions of 40~60 DEG C of maintenance system temperature, through filtering, 1L water washings 3 times,
500mL ethyl alcohol washs 2 times, and under nitrogen protection, 300 DEG C of roasting 3h obtain calcium sulfide；Water, ethyl alcohol and the dodecyl
In order to provide the microemulsion system of calcium sulfhydrate stabilization, the purpose of the thiocarbamide hydrogenates the purpose of benzene sulfonic acid sodium salt in order to destroy sulphur
The stability of calcium microemulsion system.
(3), by mono phosphoric acid ester ethyl ester, 1,5- naphthylenediamines, ethyl alcohol and calcium sulfide according to quality parts ratio 100：78~96：
100~120：25~30 are added in reaction kettle, and in 135~150 DEG C of temperature, mixing speed is anti-under the conditions of being 50~70r/min
Answer 1~3 h to get to modified calcium sulfide；The purpose of the mono phosphoric acid ester ethyl ester and 1,5- naphthylenediamines is in order to improve calcium sulfide
Dispersibility and polyethylene anti-flammability.
(4), by PVC pellets, epoxychloropropane, sodium hydroxide, ethyl alcohol, water and diethylin for methyltriethoxysilane
According to quality parts ratio 100：15~20：3~7：15~20：3~5：2~5 are added in open mill, with open mill in temperature
140~190 DEG C of 0.5~2h of hybrid reaction are changed in 140~190 DEG C of extruding pelletizations of temperature to get to epoxychloropropane with extruder
Property PVC pellets；The purpose of the sodium hydroxide and water is for the new ring of the reactivity and catalysis that improve epoxychloropropane
Oxygroup generates.
(5), by epoxychloropropane modified PVC, modified calcium sulfide, aluminium oxide, modified calcium sulfate and 1,3,5- trimethyl -2,
4,6-（3,5- di-t-butyl -4- hydroxyphenylmethyls）Benzene is according to quality parts ratio 100：4~7：7~12：6~14：1~2 is added
Into open mill, with open mill in 140~190 DEG C of 0.5~2h of hybrid reaction of temperature, incited somebody to action for 140~190 DEG C in temperature with extruder
Modified PVC extruding pelletization is to get to modified PVC pellet.
Invention has the beneficial effects that：
1, calcium sulfate surface is modified using polyamide and polyvinyl alcohol, polyvinyl alcohol can improve the hydrophily of calcium sulfate
And increasing surface hydroxyl groups, polyamide can not only improve compatibility of the calcium sulfate in PVC, but also can improve
Calcium sulfate chemical mobility of the surface, crosslinks with modified PVC and reacts, and on the one hand can improve dispersibility of the calcium sulfate in PVC
And compatibility, it on the other hand can also improve mechanical strengths and the heat resistances such as the impact strength, tensile strength, bending strength of PVC
Energy；
2, in calcium sulfide preparation process, neopelex and diethylin can be to sulphur for methyltriethoxysilane
Calcium hydride surface modification prevents the hydrolysis of calcium sulfhydrate, and when temperature of reaction system reduces, calcium sulfhydrate and thiocarbamide are in water-second
Solubility in alcohol-butanol continuously decreases, and forms the calcium sulfhydrate and compound of size uniformity, under nitrogen protection, sulphur
Calcium hydride and compound generate nanometer calcium sulfide at high temperature, and nanometer calcium sulfide has excellent ultraviolet shielding effect,
The excellent UV resistant performances of PVC can be assigned；
3, mono phosphoric acid ester ethyl ester and 1,5- naphthylenediamines not only can be very good dispersed sulfur calcium, and polycondensation reaction can also occur, raw
At mono phosphoric acid ester ethyl ester -1,5- naphthylenediamine polymer with high flame resistance, it is excellent that this polymer can not only assign PVC
Flame retardant property and heat resistance can also improve dispersibility and compatibility of the calcium sulfide in PVC；
4, due to crazing toughening mechanism, modified calcium sulfide can improve the mechanical strength and toughness of PVC；
5, epoxychloropropane modified PVC pellets, can increase the chemism of PVC surface, crosslink and react with modified filler,
Improve dispersibility, compatibility, chemical stability and mechanical strength of the modified filler in PVC；
6, the thermal conductivity of alumina fibre is preferable, can not only improve the thermal conductivity of PVC, can be with the mechanical strength of Reinforced PVC.
Specific implementation mode
The specific implementation mode of the invention is described with reference to embodiment, to be better understood from the invention.
Embodiment 1
A kind of modified PVC, preparation method includes the following steps：
(1), 100 parts of calcium sulfate, 32 parts of ethyl alcohol, 13 parts of polyvinyl alcohol and 12 parts of polyamides are weighed to be added in reactor,
Mixing speed is 75r/min, reacts 1.5h under the conditions of 86 DEG C of maintenance system temperature, and at 90 DEG C, -0.07MPa is evaporated under reduced pressure 2h,
120 DEG C of dry 2h obtain modified calcium sulfate；
(2), 100 parts of calcium sulfhydrates, 80 parts of water, 170 parts of ethyl alcohol, 18 parts of neopelexes, 9 parts of diethylin generations are weighed
Methyltriethoxysilane and 40 parts of thiocarbamides are added in reaction kettle, mixing speed 130r/min, 50 DEG C of maintenance system temperature
Under the conditions of react 3h, washed 2 times through filtering, 1L water washings 3 times, 500mL ethyl alcohol, under nitrogen protection, 300 DEG C of roasting 3h are obtained
To calcium sulfide；
(3), 100 parts of mono phosphoric acid ester ethyl esters, 86 parts of 1,5- naphthylenediamines, 110 parts of ethyl alcohol and 27 parts of calcium sulfides are weighed and are added to reaction
In kettle, in 140 DEG C of temperature, mixing speed reacts 2 h to get to modified calcium sulfide under the conditions of being 62r/min；
(4), 100 parts of PVC pellets, 17 parts of epoxychloropropane, 5 parts of sodium hydroxides, 18 parts of ethyl alcohol, 4 parts of water and 3 parts of diethylamine are weighed
Base is added to for methyltriethoxysilane in open mill, with open mill in 160 DEG C of hybrid reaction 0.8h of temperature, is existed with extruder
160 DEG C of extruding pelletizations of temperature are to get to epoxychloropropane modified PVC pellets；
(5), 100 parts of epoxychloropropane modified PVC, 6 parts of modified calcium sulfides, 10 parts of aluminium oxide, 12 parts of modified calcium sulfate and 2 are weighed
Part 1,3,5- trimethyls -2,4,6-（3,5- di-t-butyl -4- hydroxyphenylmethyls）Benzene is added in open mill, with open mill in temperature
Spend 165 DEG C of hybrid reaction 0.6h, with extruder in 165 DEG C of temperature by modified PVC extruding pelletization to get to modified PVC pellet.
Embodiment 2
A kind of modified PVC, preparation method includes the following steps：
(1), 100 parts of calcium sulfate, 30 parts of ethyl alcohol, 10 parts of polyvinyl alcohol and 8 parts of polyamides are weighed to be added in reactor, are stirred
It is 70r/min to mix speed, reacts 1h under the conditions of 80 DEG C of maintenance system temperature, and at 90 DEG C, -0.07MPa is evaporated under reduced pressure 2h, 120 DEG C
Dry 2h obtains modified calcium sulfate；
(2), 100 parts of calcium sulfhydrates, 70 parts of water, 150 parts of ethyl alcohol, 10 parts of neopelexes, 7 parts of diethylin generations are weighed
Methyltriethoxysilane and 30 parts of thiocarbamides are added in reaction kettle, mixing speed 120r/min, 40 DEG C of maintenance system temperature
Under the conditions of react 2h, washed 2 times through filtering, 1L water washings 3 times, 500mL ethyl alcohol, under nitrogen protection, 300 DEG C of roasting 3h are obtained
To calcium sulfide；
(3), 100 parts of mono phosphoric acid ester ethyl esters, 78 parts of 1,5- naphthylenediamines, 100 parts of ethyl alcohol and 25 parts of calcium sulfides are weighed and are added to reaction
In kettle, in 135 DEG C of temperature, mixing speed reacts 1 h to get to modified calcium sulfide under the conditions of being 50r/min；
(4), 100 parts of PVC pellets, 15 parts of epoxychloropropane, 3 parts of sodium hydroxides, 15 parts of ethyl alcohol, 3 parts of water and 2 parts of diethylamine are weighed
Base is added to for methyltriethoxysilane in open mill, with open mill in 140 DEG C of hybrid reaction 0.5h of temperature, is existed with extruder
140 DEG C of extruding pelletizations of temperature are to get to epoxychloropropane modified PVC pellets；
(5), 100 parts of epoxychloropropane modified PVC, 4 parts of modified calcium sulfides, 7 parts of aluminium oxide, 6 parts of modified calcium sulfate and 1 part are weighed
1,3,5- trimethyl -2,4,6-（3,5- di-t-butyl -4- hydroxyphenylmethyls）Benzene is added in open mill, with open mill in temperature
140 DEG C of hybrid reaction 0.5h, with extruder in 140 DEG C of temperature by modified PVC extruding pelletization to get to modified PVC pellet.
Embodiment 3
A kind of modified PVC, preparation method includes the following steps：
(1), 100 parts of calcium sulfate, 35 parts of ethyl alcohol, 15 parts of polyvinyl alcohol and 13 parts of polyamides are weighed to be added in reactor,
Mixing speed is 80r/min, reacts 3h under the conditions of 100 DEG C of maintenance system temperature, and at 90 DEG C, -0.07MPa is evaporated under reduced pressure 2h,
120 DEG C of dry 2h obtain modified calcium sulfate；
(2), 100 parts of calcium sulfhydrates, 100 parts of water, 200 parts of ethyl alcohol, 20 parts of neopelexes, 13 parts of diethylin are weighed
It is added in reaction kettle for methyltriethoxysilane and 50 parts of thiocarbamides, mixing speed 150r/min, maintenance system temperature 60
4h is reacted under the conditions of DEG C, and 2 times are washed through filtering, 1L water washings 3 times, 500mL ethyl alcohol, under nitrogen protection, 300 DEG C of roasting 3h,
Obtain calcium sulfide；
(3), 100 parts of mono phosphoric acid ester ethyl esters, 96 parts of 1,5- naphthylenediamines, 120 parts of ethyl alcohol and 30 parts of calcium sulfides are weighed and are added to reaction
In kettle, in 150 DEG C of temperature, mixing speed reacts 3 h to get to modified calcium sulfide under the conditions of being 70r/min；
(4), 100 parts of PVC pellets, 20 parts of epoxychloropropane, 7 parts of sodium hydroxides, 20 parts of ethyl alcohol, 5 parts of water and 5 parts of diethylamine are weighed
Base is added to for methyltriethoxysilane in open mill, with open mill in 190 DEG C of hybrid reaction 2h of temperature, with extruder in temperature
190 DEG C of extruding pelletizations are spent to get to epoxychloropropane modified PVC pellets；
(5), 100 parts of epoxychloropropane modified PVC, 7 parts of modified calcium sulfides, 12 parts of aluminium oxide, 14 parts of modified calcium sulfate and 2 are weighed
Part 1,3,5- trimethyls -2,4,6-（3,5- di-t-butyl -4- hydroxyphenylmethyls）Benzene is added in open mill, with open mill in temperature
Spend 190 DEG C of hybrid reaction 2h, with extruder in 190 DEG C of temperature by modified PVC extruding pelletization to get to modified PVC pellet.
Embodiment 4
A kind of modified PVC, preparation method includes the following steps：
(1), 100 parts of calcium sulfate, 31 parts of ethyl alcohol, 14 parts of polyvinyl alcohol and 12 parts of polyamides are weighed to be added in reactor,
Mixing speed is 75r/min, reacts 2h under the conditions of 90 DEG C of maintenance system temperature, and at 90 DEG C, -0.07MPa is evaporated under reduced pressure 2h, 120
DEG C dry 2h, obtains modified calcium sulfate；
(2), 100 parts of calcium sulfhydrates, 80 parts of water, 160 parts of ethyl alcohol, 19 parts of neopelexes, 12 parts of diethylin are weighed
It is added in reaction kettle for methyltriethoxysilane and 40 parts of thiocarbamides, mixing speed 140r/min, maintenance system temperature 50
3h is reacted under the conditions of DEG C, and 2 times are washed through filtering, 1L water washings 3 times, 500mL ethyl alcohol, under nitrogen protection, 300 DEG C of roasting 3h,
Obtain calcium sulfide；
(3), 100 parts of mono phosphoric acid ester ethyl esters, 80 parts of 1,5- naphthylenediamines, 110 parts of ethyl alcohol and 26 parts of calcium sulfides are weighed and are added to reaction
In kettle, in 140 DEG C of temperature, mixing speed reacts 2 h to get to modified calcium sulfide under the conditions of being 60r/min；
(4), 100 parts of PVC pellets, 16 parts of epoxychloropropane, 6 parts of sodium hydroxides, 19 parts of ethyl alcohol, 4 parts of water and 3 parts of diethylamine are weighed
Base is added to for methyltriethoxysilane in open mill, with open mill in 185 DEG C of hybrid reaction 0.7h of temperature, is existed with extruder
185 DEG C of extruding pelletizations of temperature are to get to epoxychloropropane modified PVC pellets；
(5), 100 parts of epoxychloropropane modified PVC, 6 parts of modified calcium sulfides, 9 parts of aluminium oxide, 13 parts of modified calcium sulfate and 1 are weighed
Part 1,3,5- trimethyls -2,4,6-（3,5- di-t-butyl -4- hydroxyphenylmethyls）Benzene is added in open mill, with open mill in temperature
Spend 185 DEG C of hybrid reaction 0.5h, with extruder in 185 DEG C of temperature by modified PVC extruding pelletization to get to modified PVC pellet.
Embodiment 5
A kind of modified PVC, preparation method includes the following steps：
(1), 100 parts of calcium sulfate, 32 parts of ethyl alcohol, 11 parts of polyvinyl alcohol and 9 parts of polyamides are weighed to be added in reactor, are stirred
It is 72r/min to mix speed, reacts 1.2h under the conditions of 83 DEG C of maintenance system temperature, and at 90 DEG C, -0.07MPa is evaporated under reduced pressure 2h, 120
DEG C dry 2h, obtains modified calcium sulfate；
(2), 100 parts of calcium sulfhydrates, 79 parts of water, 160 parts of ethyl alcohol, 13 parts of neopelexes, 8 parts of diethylin generations are weighed
Methyltriethoxysilane and 33 parts of thiocarbamides are added in reaction kettle, mixing speed 136r/min, 46 DEG C of maintenance system temperature
Under the conditions of react 2.5h, wash 2 times through filtering, 1L water washings 3 times, 500mL ethyl alcohol, under nitrogen protection, 300 DEG C of roasting 3h,
Obtain calcium sulfide；
(3), 100 parts of mono phosphoric acid ester ethyl esters, 79 parts of 1,5- naphthylenediamines, 103 parts of ethyl alcohol and 27 parts of calcium sulfides are weighed and are added to reaction
In kettle, in 136 DEG C of temperature, mixing speed reacts 1.2 h to get to modified calcium sulfide under the conditions of being 54r/min；
(4), 100 parts of PVC pellets, 17 parts of epoxychloropropane, 5 parts of sodium hydroxides, 17 parts of ethyl alcohol, 4 parts of water and 4 parts of diethylamine are weighed
Base is added to for methyltriethoxysilane in open mill, with open mill in 143 DEG C of hybrid reaction 1.9h of temperature, is existed with extruder
143 DEG C of extruding pelletizations of temperature are to get to epoxychloropropane modified PVC pellets；
(5), weigh 100 parts of epoxychloropropane modified PVC, 5 parts of modified calcium sulfides, 10 parts of aluminium oxide, 13 parts of modified calcium sulfate and
1.2 part 1,3,5- trimethyls -2,4,6-（3,5- di-t-butyl -4- hydroxyphenylmethyls）Benzene is added in open mill, uses open mill
In 145 DEG C of hybrid reaction 1.8h of temperature, with extruder in 145 DEG C of temperature by modified PVC extruding pelletization to get to modified PVC grain
Material.
Embodiment 6
A kind of modified PVC, preparation method includes the following steps：
(1), 100 parts of calcium sulfate, 34 parts of ethyl alcohol, 14 parts of polyvinyl alcohol and 10 parts of polyamides are weighed to be added in reactor,
Mixing speed is 73r/min, reacts 1.6h under the conditions of 95 DEG C of maintenance system temperature, and at 90 DEG C, -0.07MPa is evaporated under reduced pressure 2h,
120 DEG C of dry 2h obtain modified calcium sulfate；
(2), 100 parts of calcium sulfhydrates, 97 parts of water, 180 parts of ethyl alcohol, 15 parts of neopelexes, 8 parts of diethylin generations are weighed
Methyltriethoxysilane and 37 parts of thiocarbamides are added in reaction kettle, mixing speed 134r/min, 45 DEG C of maintenance system temperature
Under the conditions of react 2.7h, wash 2 times through filtering, 1L water washings 3 times, 500mL ethyl alcohol, under nitrogen protection, 300 DEG C of roasting 3h,
Obtain calcium sulfide；
(3), 100 parts of mono phosphoric acid ester ethyl esters, 82 parts of 1,5- naphthylenediamines, 107 parts of ethyl alcohol and 28 parts of calcium sulfides are weighed and are added to reaction
In kettle, in 142 DEG C of temperature, mixing speed reacts 2.3 h to get to modified calcium sulfide under the conditions of being 55r/min；
(4), 100 parts of PVC pellets, 16 parts of epoxychloropropane, 4.3 parts of sodium hydroxides, 18 parts of ethyl alcohol, 3.7 parts of water and 2.3 parts are weighed
Diethylin is added to for methyltriethoxysilane in open mill, with open mill in 150 DEG C of hybrid reaction 1.6h of temperature, with squeezing
Go out machine in 150 DEG C of extruding pelletizations of temperature to get to epoxychloropropane modified PVC pellets；
(5), weigh 100 parts of epoxychloropropane modified PVC, 5.3 parts of modified calcium sulfides, 9 parts of aluminium oxide, 7 parts of modified calcium sulfate and
1.5 part 1,3,5- trimethyls -2,4,6-（3,5- di-t-butyl -4- hydroxyphenylmethyls）Benzene is added in open mill, uses open mill
In 155 DEG C of hybrid reaction 1.5h of temperature, with extruder in 155 DEG C of temperature by modified PVC extruding pelletization to get to modified PVC grain
Material.
Embodiment 7
A kind of modified PVC, preparation method includes the following steps：
(1), 100 parts of calcium sulfate, 34 parts of ethyl alcohol, 14 parts of polyvinyl alcohol and 11 parts of polyamides are weighed to be added in reactor,
Mixing speed is 73r/min, reacts 2.9h under the conditions of 86 DEG C of maintenance system temperature, and at 90 DEG C, -0.07MPa is evaporated under reduced pressure 2h,
120 DEG C of dry 2h obtain modified calcium sulfate；
(2), 100 parts of calcium sulfhydrates, 94 parts of water, 160 parts of ethyl alcohol, 14 parts of neopelexes, 9 parts of diethylin generations are weighed
Methyltriethoxysilane and 38 parts of thiocarbamides are added in reaction kettle, mixing speed 137r/min, 48 DEG C of maintenance system temperature
Under the conditions of react 2.5h, wash 2 times through filtering, 1L water washings 3 times, 500mL ethyl alcohol, under nitrogen protection, 300 DEG C of roasting 3h,
Obtain calcium sulfide；
(3), 100 parts of mono phosphoric acid ester ethyl esters, 86 parts of 1,5- naphthylenediamines, 112 parts of ethyl alcohol and 28 parts of calcium sulfides are weighed and are added to reaction
In kettle, in 139 DEG C of temperature, mixing speed reacts 1.7 h to get to modified calcium sulfide under the conditions of being 58r/min；
(4), 100 parts of PVC pellets, 18 parts of epoxychloropropane, 4 parts of sodium hydroxides, 18 parts of ethyl alcohol, 4.2 parts of water and 3.4 part two are weighed
Ethylamino- is added to for methyltriethoxysilane in open mill, with open mill in 155 DEG C of hybrid reaction 1.3h of temperature, with extrusion
Machine is in 155 DEG C of extruding pelletizations of temperature to get to epoxychloropropane modified PVC pellets；
(5), weigh 100 parts of epoxychloropropane modified PVC, 6 parts of modified calcium sulfides, 10 parts of aluminium oxide, 9 parts of modified calcium sulfate and
1.3 part 1,3,5- trimethyls -2,4,6-（3,5- di-t-butyl -4- hydroxyphenylmethyls）Benzene is added in open mill, uses open mill
In 160 DEG C of hybrid reaction 1.1h of temperature, with extruder in 160 DEG C of temperature by modified PVC extruding pelletization to get to modified PVC grain
Material.
Embodiment 8
A kind of modified PVC, preparation method includes the following steps：
(1), 100 parts of calcium sulfate, 33 parts of ethyl alcohol, 14 parts of polyvinyl alcohol and 9 parts of polyamides are weighed to be added in reactor, are stirred
It is 75r/min to mix speed, reacts 2.6h under the conditions of 97 DEG C of maintenance system temperature, and at 90 DEG C, -0.07MPa is evaporated under reduced pressure 2h, 120
DEG C dry 2h, obtains modified calcium sulfate；
(2), 100 parts of calcium sulfhydrates, 84 parts of water, 170 parts of ethyl alcohol, 14 parts of neopelexes, 13 parts of diethylin are weighed
It is added in reaction kettle for methyltriethoxysilane and 38 parts of thiocarbamides, mixing speed 128r/min, maintenance system temperature 46
3h is reacted under the conditions of DEG C, and 2 times are washed through filtering, 1L water washings 3 times, 500mL ethyl alcohol, under nitrogen protection, 300 DEG C of roasting 3h,
Obtain calcium sulfide；
(3), 100 parts of mono phosphoric acid ester ethyl esters, 85 parts of 1,5- naphthylenediamines, 107 parts of ethyl alcohol and 29 parts of calcium sulfides are weighed and are added to reaction
In kettle, in 143 DEG C of temperature, mixing speed reacts 1.6 h to get to modified calcium sulfide under the conditions of being 66r/min；
(4), 100 parts of PVC pellets, 17 parts of epoxychloropropane, 5.7 parts of sodium hydroxides, 18 parts of ethyl alcohol, 4.3 parts of water and 3.2 parts are weighed
Diethylin is added to for methyltriethoxysilane in open mill, with open mill in 160 DEG C of hybrid reaction 1.3h of temperature, with squeezing
Go out machine in 160 DEG C of extruding pelletizations of temperature to get to epoxychloropropane modified PVC pellets；
(5), 100 parts of epoxychloropropane modified PVC, 5.3 parts of modified calcium sulfides, 9.3 parts of aluminium oxide, 7.5 parts of modified sulfuric acid are weighed
Calcium and 1.4 part 1,3,5- trimethyls -2,4,6-（3,5- di-t-butyl -4- hydroxyphenylmethyls）Benzene is added in open mill, with opening
Mill in 163 DEG C of hybrid reaction 0.9h of temperature, with extruder in 163 DEG C of temperature by modified PVC extruding pelletization to get to modification
PVC pellets.
Embodiment 9
A kind of modified PVC, preparation method includes the following steps：
(1), 100 parts of calcium sulfate, 32 parts of ethyl alcohol, 13 parts of polyvinyl alcohol and 10 parts of polyamides are weighed to be added in reactor,
Mixing speed is 76r/min, reacts 1.4h under the conditions of 88 DEG C of maintenance system temperature, and at 90 DEG C, -0.07MPa is evaporated under reduced pressure 2h,
120 DEG C of dry 2h obtain modified calcium sulfate；
(2), 100 parts of calcium sulfhydrates, 77 parts of water, 174 parts of ethyl alcohol, 11 parts of neopelexes, 8 parts of diethylin generations are weighed
Methyltriethoxysilane and 38 parts of thiocarbamides are added in reaction kettle, mixing speed 141r/min, 55 DEG C of maintenance system temperature
Under the conditions of react 3.6h, wash 2 times through filtering, 1L water washings 3 times, 500mL ethyl alcohol, under nitrogen protection, 300 DEG C of roasting 3h,
Obtain calcium sulfide；
(3), 100 parts of mono phosphoric acid ester ethyl esters, 90 parts of 1,5- naphthylenediamines, 111 parts of ethyl alcohol and 29 parts of calcium sulfides are weighed and are added to reaction
In kettle, in 138 DEG C of temperature, mixing speed reacts 2.2 h to get to modified calcium sulfide under the conditions of being 63r/min；
(4), 100 parts of PVC pellets, 19 parts of epoxychloropropane, 6 parts of sodium hydroxides, 17 parts of ethyl alcohol, 4 parts of water and 4 parts of diethylamine are weighed
Base is added to for methyltriethoxysilane in open mill, with open mill in 170 DEG C of hybrid reaction 0.8h of temperature, is existed with extruder
170 DEG C of extruding pelletizations of temperature are to get to epoxychloropropane modified PVC pellets；
(5), 100 parts of epoxychloropropane modified PVC, 6 parts of modified calcium sulfides, 11 parts of aluminium oxide, 12 parts of modified calcium sulfate and 2 are weighed
Part 1,3,5- trimethyls -2,4,6-（3,5- di-t-butyl -4- hydroxyphenylmethyls）Benzene is added in open mill, with open mill in temperature
Spend 180 DEG C of hybrid reaction 0.7h, with extruder in 180 DEG C of temperature by modified PVC extruding pelletization to get to modified PVC pellet.
Embodiment 10
A kind of modified PVC, preparation method includes the following steps：
(1), 100 parts of calcium sulfate, 33 parts of ethyl alcohol, 14 parts of polyvinyl alcohol and 8.6 parts of polyamides are weighed to be added in reactor,
Mixing speed is 75r/min, reacts 1.9h under the conditions of 97 DEG C of maintenance system temperature, and at 90 DEG C, -0.07MPa is evaporated under reduced pressure 2h,
120 DEG C of dry 2h obtain modified calcium sulfate；
(2), 100 parts of calcium sulfhydrates, 93 parts of water, 182 parts of ethyl alcohol, 19 parts of neopelexes, 9 parts of diethylin generations are weighed
Methyltriethoxysilane and 37 parts of thiocarbamides are added in reaction kettle, mixing speed 143r/min, 54 DEG C of maintenance system temperature
Under the conditions of react 3.2h, wash 2 times through filtering, 1L water washings 3 times, 500mL ethyl alcohol, under nitrogen protection, 300 DEG C of roasting 3h,
Obtain calcium sulfide；
(3), 100 parts of mono phosphoric acid ester ethyl esters, 92 parts of 1,5- naphthylenediamines, 119 parts of ethyl alcohol and 26 parts of calcium sulfides are weighed and are added to reaction
In kettle, in 143 DEG C of temperature, mixing speed reacts 2.4 h to get to modified calcium sulfide under the conditions of being 57r/min；
(4), 100 parts of PVC pellets, 16 parts of epoxychloropropane, 6 parts of sodium hydroxides, 18 parts of ethyl alcohol, 4.5 parts of water and 3.7 part two are weighed
Ethylamino- is added to for methyltriethoxysilane in open mill, with open mill in 170 DEG C of hybrid reaction 0.8h of temperature, with extrusion
Machine is in 170 DEG C of extruding pelletizations of temperature to get to epoxychloropropane modified PVC pellets；
(5), weigh 100 parts of epoxychloropropane modified PVC, 5 parts of modified calcium sulfides, 12 parts of aluminium oxide, 9 parts of modified calcium sulfate and
1.5 part 1,3,5- trimethyls -2,4,6-（3,5- di-t-butyl -4- hydroxyphenylmethyls）Benzene is added in open mill, uses open mill
In 175 DEG C of hybrid reaction 0.7h of temperature, with extruder in 175 DEG C of temperature by modified PVC extruding pelletization to get to modified PVC grain
Material.
Embodiment 11
A kind of modified PVC, preparation method includes the following steps：
(1), 100 parts of calcium sulfate, 34 parts of ethyl alcohol, 12 parts of polyvinyl alcohol and 11 parts of polyamides are weighed to be added in reactor,
Mixing speed is 77r/min, reacts 2h under the conditions of 97 DEG C of maintenance system temperature, and at 90 DEG C, -0.07MPa is evaporated under reduced pressure 2h, 120
DEG C dry 2h, obtains modified calcium sulfate；
(2), 100 parts of calcium sulfhydrates, 79 parts of water, 177 parts of ethyl alcohol, 15 parts of neopelexes, 13 parts of diethylin are weighed
It is added in reaction kettle for methyltriethoxysilane and 44 parts of thiocarbamides, mixing speed 144r/min, maintenance system temperature 55
3.3h is reacted under the conditions of DEG C, and 2 times, under nitrogen protection, 300 DEG C of roastings are washed through filtering, 1L water washings 3 times, 500mL ethyl alcohol
3h obtains calcium sulfide；
(3), 100 parts of mono phosphoric acid ester ethyl esters, 88 parts of 1,5- naphthylenediamines, 113 parts of ethyl alcohol and 26 parts of calcium sulfides are weighed and are added to reaction
In kettle, in 140 DEG C of temperature, mixing speed reacts 2.1 h to get to modified calcium sulfide under the conditions of being 66r/min；
(4), 100 parts of PVC pellets, 18 parts of epoxychloropropane, 6 parts of sodium hydroxides, 17 parts of ethyl alcohol, 4 parts of water and 5 parts of diethylamine are weighed
Base is added to for methyltriethoxysilane in open mill, with open mill in 180 DEG C of hybrid reaction 0.5h of temperature, is existed with extruder
180 DEG C of extruding pelletizations of temperature are to get to epoxychloropropane modified PVC pellets；
(5), weigh 100 parts of epoxychloropropane modified PVC, 6 parts of modified calcium sulfides, 9 parts of aluminium oxide, 13 parts of modified calcium sulfate and
1.2 part 1,3,5- trimethyls -2,4,6-（3,5- di-t-butyl -4- hydroxyphenylmethyls）Benzene is added in open mill, uses open mill
In 185 DEG C of hybrid reaction 0.6h of temperature, with extruder in 185 DEG C of temperature by modified PVC extruding pelletization to get to modified PVC grain
Material.
Embodiment 12
A kind of modified PVC, preparation method includes the following steps：
(1), 100 parts of calcium sulfate, 34 parts of ethyl alcohol, 13 parts of polyvinyl alcohol and 10 parts of polyamides are weighed to be added in reactor,
Mixing speed is 77r/min, reacts 2h under the conditions of 95 DEG C of maintenance system temperature, and at 90 DEG C, -0.07MPa is evaporated under reduced pressure 2h, 120
DEG C dry 2h, obtains modified calcium sulfate；
(2), 100 parts of calcium sulfhydrates, 83 parts of water, 194 parts of ethyl alcohol, 16 parts of neopelexes, 12 parts of diethylin are weighed
It is added in reaction kettle for methyltriethoxysilane and 41 parts of thiocarbamides, mixing speed 143r/min, maintenance system temperature 53
3h is reacted under the conditions of DEG C, and 2 times are washed through filtering, 1L water washings 3 times, 500mL ethyl alcohol, under nitrogen protection, 300 DEG C of roasting 3h,
Obtain calcium sulfide；
(3), 100 parts of mono phosphoric acid ester ethyl esters, 86 parts of 1,5- naphthylenediamines, 110 parts of ethyl alcohol and 27 parts of calcium sulfides are weighed and are added to reaction
In kettle, in 138 DEG C of temperature, mixing speed reacts 2 h to get to modified calcium sulfide under the conditions of being 62r/min；
(4), 100 parts of PVC pellets, 19 parts of epoxychloropropane, 5 parts of sodium hydroxides, 17 parts of ethyl alcohol, 5 parts of water and 3 parts of diethylamine are weighed
Base is added to for methyltriethoxysilane in open mill, with open mill in 164 DEG C of hybrid reaction 0.9h of temperature, is existed with extruder
164 DEG C of extruding pelletizations of temperature are to get to epoxychloropropane modified PVC pellets；
(5), 100 parts of epoxychloropropane modified PVC, 6 parts of modified calcium sulfides, 12 parts of aluminium oxide, 14 parts of modified calcium sulfate and 1 are weighed
Part 1,3,5- trimethyls -2,4,6-（3,5- di-t-butyl -4- hydroxyphenylmethyls）Benzene is added in open mill, with open mill in temperature
Spend 168 DEG C of hybrid reaction 0.9h, with extruder in 168 DEG C of temperature by modified PVC extruding pelletization to get to modified PVC pellet.
The performance parameter of modified PVC made from 1 embodiment 1 of table
| Embodiment 1 | |
| Ultraviolet-shielding type | It is excellent |
| Oxygen index (OI) % | 37 |
| Thermal coefficient/W/m.K | 0.24 |
| Tensile strength/MPa | 55 |
| Zero load maximum operation (service) temperature/DEG C | 87 |
| Molding shrinkage/% | 0.1 |
The above is the preferred embodiment of the invention, it is noted that for those skilled in the art,
Under the premise of not departing from the inventive principle, several improvements and modifications can also be made, these improvements and modifications are also considered as the hair
Bright protection domain.
Claims (2)
1. a kind of preparation method of modified PVC, it is characterised in that：Including following raw material components：Epoxychloropropane modified PVC, change
Property calcium sulfide, aluminium oxide, modified calcium sulfate and 1,3,5- trimethyls -2,4,6-（3,5- di-t-butyl -4- hydroxyphenylmethyls）Benzene,
The epoxychloropropane modified PVC, modified calcium sulfide, aluminium oxide, modified calcium sulfate and 1,3,5- trimethyls -2,4,6-（3,
5- di-t-butyl -4- hydroxyphenylmethyls）The quality parts ratio of benzene is 100：4~7：7~12：6~14：1~2 is added to open mill
In, with open mill in 140~190 DEG C of 0.5~2h of hybrid reaction of temperature, with extruder in 140~190 DEG C of temperature by modified PVC
Extruding pelletization, wherein the epoxychloropropane modified PVC pellets by PVC pellets, epoxychloropropane, sodium hydroxide, ethyl alcohol,
Water and diethylin are reacted for methyltriethoxysilane to be made, the PVC pellets, epoxychloropropane, sodium hydroxide, second
Alcohol, water and diethylin are 100 for the quality parts ratio of methyltriethoxysilane：15~20：3~7：15~20：3~5：2
~5 are added in open mill, with open mill in 140~190 DEG C of 0.5~2h of hybrid reaction of temperature, with extruder temperature 140~
190 DEG C of extruding pelletizations, the modification calcium sulfide is reacted by mono phosphoric acid ester ethyl ester, 1,5- naphthylenediamines, ethyl alcohol and calcium sulfide to be made,
The mono phosphoric acid ester ethyl ester, 1,5- naphthylenediamines, ethyl alcohol and calcium sulfide quality parts ratio be 100：78~96：100~120：
25~30, the calcium sulfide is by calcium sulfhydrate, water, ethyl alcohol, neopelex, diethylin for methyl triethoxy
Silane and thiocarbamide reaction are made, and the calcium sulfhydrate, water, ethyl alcohol, neopelex, diethylin are for three second of methyl
Oxysilane and the quality parts ratio of thiocarbamide are 100：70~100：150~200：10~20：7~13：30~50 are added to instead
It answers in kettle, mixing speed is 120~150r/min, 2~4h is reacted under the conditions of 40~60 DEG C of maintenance system temperature, through filtering, 1L
Water washing 3 times, 500mL ethyl alcohol wash 2 times, under nitrogen protection, 300 DEG C of roasting 3h, the modification calcium sulfate by calcium sulfate,
Ethyl alcohol, polyvinyl alcohol and polyamide reaction are made, the matter of the calcium sulfate, ethyl alcohol, polyvinyl alcohol and polyamide
It is 100 to measure portion rate：30~35：10~15：8~13 are added in reactor, and mixing speed is 70~80r/min, maintains body
It is that 1~3h is reacted under the conditions of 80~100 DEG C of temperature, at 90 DEG C, -0.07MPa is evaporated under reduced pressure 2h, 120 DEG C of dry 2h.
2. a kind of preparation method of modified PVC according to claim 1, it is characterised in that：The modification calcium sulfide is
Made from following preparation method：By mono phosphoric acid ester ethyl ester, 1,5- naphthylenediamines, ethyl alcohol and calcium sulfide according to quality parts ratio 100：
79~86：103~110：26~29 are added in reaction kettle, and in 136~143 DEG C of temperature, mixing speed is 54~66r/min
Under the conditions of react 1.2~2.3 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810158055.3A CN108456388A (en) | 2016-07-18 | 2016-07-18 | A kind of filling-modified PVC of calcium sulfide and preparation method thereof |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810158055.3A CN108456388A (en) | 2016-07-18 | 2016-07-18 | A kind of filling-modified PVC of calcium sulfide and preparation method thereof |
| CN201610561250.1A CN106189004B (en) | 2016-07-18 | 2016-07-18 | A kind of modified PVC and preparation method thereof |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610561250.1A Division CN106189004B (en) | 2016-07-18 | 2016-07-18 | A kind of modified PVC and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108456388A true CN108456388A (en) | 2018-08-28 |
Family
ID=57475037
Family Applications (4)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610561250.1A Active CN106189004B (en) | 2016-07-18 | 2016-07-18 | A kind of modified PVC and preparation method thereof |
| CN201810158055.3A Pending CN108456388A (en) | 2016-07-18 | 2016-07-18 | A kind of filling-modified PVC of calcium sulfide and preparation method thereof |
| CN201810158059.1A Withdrawn CN108285601A (en) | 2016-07-18 | 2016-07-18 | A kind of calcium sulfate modified PVC and preparation method thereof |
| CN201810158071.2A Withdrawn CN108456389A (en) | 2016-07-18 | 2016-07-18 | A kind of calcium sulfide modified PVC and preparation method thereof |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610561250.1A Active CN106189004B (en) | 2016-07-18 | 2016-07-18 | A kind of modified PVC and preparation method thereof |
Family Applications After (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810158059.1A Withdrawn CN108285601A (en) | 2016-07-18 | 2016-07-18 | A kind of calcium sulfate modified PVC and preparation method thereof |
| CN201810158071.2A Withdrawn CN108456389A (en) | 2016-07-18 | 2016-07-18 | A kind of calcium sulfide modified PVC and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (4) | CN106189004B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475725A (en) * | 2009-01-09 | 2009-07-08 | 深圳市领亚电子有限公司 | Ultraviolet resistant polychloroethylene composition for electric wire and cable, and preparation |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104312139A (en) * | 2014-10-25 | 2015-01-28 | 合肥市安山涂层织物有限公司 | Polished anti-corrosion synthetic leather slurry and preparation method thereof |
| CN104479247A (en) * | 2014-12-10 | 2015-04-01 | 安徽国通高新管业股份有限公司 | Modified reinforced high-impact-resistance PVC-M (modified polyvinyl chloride) double-wall corrugated pipe |
-
2016
- 2016-07-18 CN CN201610561250.1A patent/CN106189004B/en active Active
- 2016-07-18 CN CN201810158055.3A patent/CN108456388A/en active Pending
- 2016-07-18 CN CN201810158059.1A patent/CN108285601A/en not_active Withdrawn
- 2016-07-18 CN CN201810158071.2A patent/CN108456389A/en not_active Withdrawn
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475725A (en) * | 2009-01-09 | 2009-07-08 | 深圳市领亚电子有限公司 | Ultraviolet resistant polychloroethylene composition for electric wire and cable, and preparation |
Non-Patent Citations (2)
| Title |
|---|
| 林茵等主编: "《有机化学辞典》", 30 September 2006, 远方出版社 * |
| 王道等主编: "《环境有害化学品实用手册》", 31 December 2007, 中国环境科学出版社 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106189004A (en) | 2016-12-07 |
| CN108285601A (en) | 2018-07-17 |
| CN106189004B (en) | 2018-05-11 |
| CN108456389A (en) | 2018-08-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108192027A (en) | A kind of polar polypropylene graft and preparation method thereof | |
| CN103408948A (en) | Rubber composition and application thereof | |
| CN107474442A (en) | A kind of PVC board and its preparation technology | |
| CN105440399A (en) | Polyvinyl wood-plastic composite and preparation method thereof | |
| CN105949662A (en) | Flame-retardant jacket material for low-medium voltage cable | |
| CN105924800B (en) | A kind of MODIFIED PP R and preparation method thereof | |
| CN106188975B (en) | A kind of soft high transparent and fire-retardant heat-resistant polyvinyl chloride material of spy and preparation method thereof | |
| CN103360661B (en) | A kind of Oil-Resistant Cable Sheath | |
| CN104292391A (en) | Melting production method for unsaturated anhydride grafted chlorinated polyethylene | |
| CN108456388A (en) | A kind of filling-modified PVC of calcium sulfide and preparation method thereof | |
| CN107082956A (en) | A kind of talcum powder master batch | |
| CN110655734A (en) | High-toughness impact-resistant polyvinyl chloride material and preparation method thereof | |
| CN106188750B (en) | A kind of modified poly ethylene and preparation method thereof | |
| CN104693661A (en) | Preparation method of corrosion-resistant conveyor belt | |
| CN107446216A (en) | A kind of alkaline-resisting polythene material and preparation method thereof | |
| CN106243550A (en) | A kind of inorganic material-modified polrvinyl chloride and preparation method thereof | |
| CN109161115A (en) | A kind of compound pencil material of micro foam polystyrene | |
| CN106188843B (en) | A kind of modified polypropene and preparation method thereof | |
| CN110964264A (en) | Heat-resistant MPP cable protection pipe and preparation method thereof | |
| CN108976650A (en) | A kind of environment-friendlyweather-proof weather-proof type high light transmission PVC pipeline | |
| CN106957518A (en) | Shell alloy material after a kind of high-ductility LCD TV | |
| CN107254175A (en) | A kind of improved low-smoke halogen-free cable gum cover and preparation method thereof | |
| CN112940378A (en) | Processing method of ultra-high molecular PE pipe | |
| CN108503912A (en) | Battery flame retardant plastic material shell and preparation method thereof | |
| CN106380673A (en) | Modified PE (poly ethylene) and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20180828 |