CN1052987C - Method for preparing modified styrene butadiene rubber powder used as toughness-increased agent for poly vinyl chloride - Google Patents
Method for preparing modified styrene butadiene rubber powder used as toughness-increased agent for poly vinyl chloride Download PDFInfo
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- CN1052987C CN1052987C CN97111343A CN97111343A CN1052987C CN 1052987 C CN1052987 C CN 1052987C CN 97111343 A CN97111343 A CN 97111343A CN 97111343 A CN97111343 A CN 97111343A CN 1052987 C CN1052987 C CN 1052987C
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Abstract
The present invention relates to a method for preparing modified butylbenzene rubber powder used for plasticizing rigid polyvinyl chloride. Used rubber is universal synthetic butylbenzene latex, and mixing monomers are added into the universal synthetic butylbenzene latex to carry out graft copolymerization reaction by pre-crosslinking or no pre-crosslinking. A macromolecular coating agent with Mn of 0.04 to 0.06 million is added into graft modification latex, and polyvalent water-soluble metal salt is used for carrying out poly crosslinking. The modified butylbenzene rubber powder used for plasticizing rigid polyvinyl chloride is obtained by filtration, washing, dehydration, screening and drying, the particle diameter of the modified butylbenzene rubber powder is smaller than 1mm, and the rubber content of the modified butylbenzene rubber powder is higher than 60%. The use amount and the kind of the mixing monomers, and reaction process conditions are properly adjusted. The modified butylbenzene rubber powder which is respectively used for plasticizing rigid polyvinyl chloride and soft polyvinyl chloride can be prepared. The plasticizing effect of the modified butylbenzene rubber powder to polyvinyl chloride is particularly marked.
Description
The present invention relates to the China Synthetic Rubber Industry field, specifically be meant the preparation method of modified styrene butadiene rubber powder used as toughness-increased agent for poly vinyl chloride.
Styrene-butadiene rubber(SBR) is one of universal synthetic rubber of present output in domestic maximum, and price is relatively low.By suitable chemical modification, can widen the Application Areas of styrene-butadiene rubber(SBR).Styrene-butadiene rubber(SBR) connects the skill copolyreaction with different monomer, can prepare the resin of different purposes, and as ABS, MBS etc., these resins can use separately, also can carry out blending and modifying with other polymkeric substance.
The properties-correcting agent of used as toughness-increased agent for poly vinyl chloride mainly contains chlorinatedpolyethylene, MBS, Powdered acrylonitrile-butadiene rubber etc. at present.Chlorinatedpolyethylene is mainly as toughness reinforcing rigid polyvinyl chloride, and MBS is as toughness reinforcing transparent polyvinyl chloride, and Powdered acrylonitrile-butadiene rubber is used for toughness reinforcing soft PVC.The two kinds of toughner output in domestic in back are few, and on the high side.
The objective of the invention is to overcome the deficiencies in the prior art part, provide a kind of and can utilize abundant, the cheap general purpose material in source, prepared modified styrene butadiene rubber powder rubber content height, polyvinyl chloride is had significant toughening effect, and the preparation method of the easy modified styrene butadiene rubber powder used as toughness-increased agent for poly vinyl chloride of method of modifying.
The objective of the invention is to reach by following measure:
Make the preparation method of toughness reinforcing rigid polyvinyl chloride, it is characterized in that its processing step and condition are as follows with modified styrene butadiene rubber powder:
Step 1: the preparation of high-molecular coating agent
(1) preparation of solution
By vinylbenzene: MALEIC ANHYDRIDE: the weight ratio of benzoyl peroxide is 100～110: the ratio that 94.2: 0.971～1.457 batching drops into toluene or toluene and hexanaphthene is in 1: 1～2 the mixed solvent, is mixed with 10～20% solution;
(2) copolyreaction
Be warming up to 60～80 ℃, reacted 2～3 hours, underpressure distillation after the solvent that adds all steams, obtains M
n=4～60,000 multipolymer;
(3) saponification
By multipolymer: the weight ratio of water is to add entry at 5: 93, and under whipped state, the sodium hydroxide or the potassium hydroxide of acid anhydrides equivalent in adding and the multipolymer, 70～80 ℃ of following saponification 2～4 hours, being coated with-4 glasss of viscosity is 15～25 seconds, pH value be 9～13 milky white to little yellow multipolymer saponification liquor, be coating;
Step 2: precrosslink reaction
Select 1502 or 1500 general SBR emulsions for use, add the cumyl hydroperoxide press on glue weight meter 0.7～2%, be warming up to 70～80 ℃ of reactions 2～5 hours, obtain gel content greater than 65% precrosslinked rubber latex;
Step 3: the graft modification of styrene-butadiene latex
Add vinylbenzene, vinyl cyanide and cumyl hydroperoxide at the prepared gel content of step 2 in greater than 65% precrosslinked rubber latex, its weight ratio is dried glue: vinylbenzene: vinyl cyanide: cumyl hydroperoxide=60～80: 30～15: 10～5: 0.6～0.30; Pre-swelling is 2～4 hours under 25～30 ℃, be that benchmark adds diethylamine tetraacethyl ferrisodium salt and rongalite again with the cumyl hydroperoxide, its weight ratio is 1: 0.1～0.3: 0.2～0.6, reacted 2～4 hours down at 25～30 ℃, be warmed up to 70～80 ℃ of reactions 1～3 hour, promptly obtain the graft modification styrene-butadiene latex;
Step 4: the powdered of modified styrene butadiene rubber
Under whipped state, to temperature is the deionized water that adds 1.5～2 times of its weight in 70～80 ℃ the modified butadiene-styrene latex, the high-molecular coating agent that adds the step 1 gained of pressing modified styrene butadiene rubber amount 2～6% again, add at last and press the calcium chloride of modified styrene butadiene rubber amount 2～6%, obtain micelle suspensoid by the crosslinked coating cohesion of coating, add anti-aging agent, stearic acid again, slaking 10～20 minutes, with this micelle suspensoid filter, wash, dewater, sieve, drying, promptly obtain toughness reinforcing rigid polyvinyl chloride modified styrene butadiene rubber powder.
Make the preparation method of toughness reinforcing soft PVC, it is characterized in that its processing step and condition are as follows with modified styrene butadiene rubber powder:
Step 1: the preparation of high-molecular coating agent
With making the preparation method of toughness reinforcing rigid polyvinyl chloride with modified styrene butadiene rubber powder;
Step 2: the graft modification of styrene-butadiene latex
In styrene-butadiene latex, add vinylbenzene without precrosslink, vinyl cyanide, butyl acrylate and cumyl hydroperoxide, its weight ratio is: by the non-crosslinked styrene-butadiene latex of dried glue: vinylbenzene: vinyl cyanide: Butyl acrylate: cumyl hydroperoxide=60～80: 20～15: 10～5: 10～0: 0.6～0.4;
Processing condition are with making the preparation method of toughness reinforcing rigid polyvinyl chloride with modified styrene butadiene rubber powder;
Step 3: the powdered of modified styrene butadiene rubber
Also, promptly obtain doing toughness reinforcing soft PVC modified styrene butadiene rubber powder with making the step 4 of toughness reinforcing rigid polyvinyl chloride with the preparation method of modified styrene butadiene rubber powder.
The present invention compared with prior art has following advantage:
(1) directly adopt existing general synthesizing butadiene styrene rubber emulsion to carry out modification, raw material sources are abundant, and cost is lower.Prepared modified styrene butadiene rubber powder rubber content has significant toughening effect up to more than 60% to polyvinyl chloride.
(2) adopt method of modifying of the present invention, can obtain the modified styrene butadiene rubber powder of interpenetrating polymer networks, gradual change, nucleocapsid structure, preparing multi-purpose polyvinyl chloride plasticizing agent, and method of modifying is easy, the reaction times short, energy-conservation, help enhancing productivity.
(3) the synthetic organic polymer coating preparation method who is adopted is easy, covered effect is good especially, this coating and modified styrene butadiene rubber have good consistency, can form uniform coating layer on the latex particle surface, when adding the multivalence water-soluble metal salt, polyvalent metal ion can carry out ion-exchange with potassium, sodium ion, makes the coating tunic become non-water-soluble cross linking membrane, and the micelle coating of cohesion is isolated.
(4) this preparation method's coating, flocculation agent add-on are few, and powdered process stabilizing, reliable does not have the tendency of big gel.The particle diameter of rubber powder is below 1mm, and particle diameter can be regulated with the add-on of coating, and powder formation rate reaches more than 99%.Gained rubber powder shelf-stable.
Table 1 is the influence of dosage of crosslinking agent to the toughening PVC erosion-resisting characteristics;
Table 2 is the influence of two kinds of monomer weight comparison toughening PVC erosion-resisting characteristicss when of monomer/rubber weight;
Table 3 is the relation of coating consumption and modification rubber school powder diameter.
The present invention is described in further detail by following embodiment:
Below among each embodiment, except that indicating the person, each component content is pure content meter, glue is all by dried glue.
Embodiment 1
Make the preparation method of toughness reinforcing rigid polyvinyl chloride with the modified styrene butadiene rubber powder end, its processing step and condition are as follows:
Step 1: the preparation of high-molecular coating agent
The vinylbenzene that at first in 150 liters of polymeric kettles, adds 2.45 kilograms of MALEIC ANHYDRIDE and 2.6 kilograms, 27.6 kilograms toluene, the toluene that again 0.0404 kg peroxygen benzoyl is dissolved in 1 kilogram adds in the polymeric kettle in the lump.Stirring is warming up to after 70 ℃, stops to stir, and the constant temperature standing and reacting rises to 80 ℃ of reactions 1 hour after 2 hours.Reaction finishes the back and distill out toluene under 80 ℃, 400-500mm mercury column negative pressure, is warming up to 120 ℃ of continuation then toluene is boiled off.About 2～3 hours of still-process makes multipolymer contain the toluene amount less than 1%, and the solvent that steams can be recycled.Distillation finishes, and adds 75 kilograms of deionized waters, is warming up to 70 ℃ in stirring.2 kg of hydrogen sodium oxides are dissolved in 18 kg water add in the polymeric kettle, saponification is 2 hours under constant temperature stirs, and pH value is transferred to 9～13, M
nBe little yellow transparent coating saponification aqueous solution of 40,000, this solution contains alternating copolymer 5%.
Step 2: precrosslink reaction
In 5 liters of reactors, add concentration and be 3.25 kilograms of 20% 1502 or 1500 styrene-butadiene latexes, stir and add the emulsion that contains 7 gram cumyl hydroperoxides down, be warming up to 70～80 ℃ of reactions 4 hours, obtain gel content greater than 65% precrosslink styrene-butadiene latex.
Step 3: the graft modification of styrene-butadiene latex
When the precrosslink styrene-butadiene latex is cooled to 30 ℃, add 262.5 gram vinylbenzene, 87.5 gram vinyl cyanide and 5.25 gram cumyl hydroperoxide emulsifying mixture liquid, pre-swelling is 2 hours under 25～30 ℃, 10% aqueous solution that adds diethylamine tetraacethyl ferrisodium salt 1.05 grams, rongalite 2.1 grams, hybrid reaction 3 hours, be warming up to 70 ℃ of reactions 1 hour, obtain modified butadiene-styrene latex.
Step 4: the powdered of modified styrene butadiene rubber
Styrene-butadiene latex is put into 20 liters of collection surfaces, thin up is 10% to consolidating thing content, add the step 1 product high-molecular coating agent saponification aqueous solution 800 grams again, at per minute is to mix 10 minutes under 200～300 commentaries on classics are stirred, spraying adds 5% calcium chloride solution 800 grams, be warming up to 80 ℃, the dispersion liquid of each 20 gram of antioxidant 264 that adds and sodium stearate, slaking 10～20 minutes, the discharging of lowering the temperature then, after filtration, washing, dehydration, sieve, dry, promptly obtain doing the modified styrene butadiene rubber powder that toughness reinforcing hard polrvinyl chloride product is used, this rubber powder consumption in rigid polyvinyl chloride is 10% o'clock, and the breach shock strength is 60～90KJ/m
2
Embodiment 2
Make the preparation method of toughness reinforcing rigid polyvinyl chloride with modified styrene butadiene rubber powder, its processing step and condition are as follows:
Step 1: with embodiment 1
Step 2: precrosslink reaction
In 5 liters of reactors, add concentration and be 3.5 kilograms of 20% 1502 or 1500 styrene-butadiene latexes, stir the emulsion that adds 7 gram cumyl hydroperoxides down, be warming up to 70～80 ℃ of reactions 4 hours, obtain gel content greater than 65% precrosslink styrene-butadiene latex.
Step 3: the graft modification of styrene-butadiene rubber(SBR)
When latex is cooled to 30 ℃, add 210 gram vinylbenzene, 90 gram vinyl cyanide and 4.5 gram cumyl hydroperoxide emulsifying mixture liquid, pre-swelling is 4 hours under 25～30 ℃, 10% aqueous solution that adds diethylamine tetraacethyl ferrisodium salt 0.9 gram and rongalite 1.8 grams, hybrid reaction 3 hours, be warming up to 70 ℃ of reactions 1 hour, obtain modified butadiene-styrene latex.
Step 4: the powdered of modification fourth rubber
This latex is put into 20 liters of gel grooves, thin up is 10% to consolidating thing content, add 1 kilogram of the step 1 product high-molecular coating agent saponification aqueous solution again, at per minute is to mix 10 minutes under 200～300 commentaries on classics are stirred, 1 kilogram of the calcium chloride solution of spraying adding 5%, be warming up to 80 ℃, adding concentration is the antioxidant 264 of 10%20 grams and the sodium stearate dispersion liquid of 20 grams, the discharging of lowering the temperature then, after filtration, washing, dehydration, sieve, drying promptly gets the another kind of modified styrene butadiene rubber powder that toughness reinforcing hard polrvinyl chloride product is used of doing, its to the toughening effect of polyvinyl chloride with embodiment 1.
Embodiment 3
Make the preparation method of toughness reinforcing soft PVC with modified styrene butadiene rubber powder, its processing step and condition are as follows:
Step 1: with embodiment 1
Step 2: the graft modification of styrene-butadiene rubber(SBR)
In 5 liters of reactors, add concentration and be 4 kilograms of 20% 1502 or 1500 styrene-butadiene latexes, the emulsion that under 20～30 ℃ of stirrings, adds 150 gram vinylbenzene, 50 gram vinyl cyanide and 4 gram cumyl hydroperoxides, mix after 1 hour, the 10% aqueous fusion liquid that adds diethylamine tetraacethyl ferrisodium salt 0.8 gram and rongalite 1.6 grams, hybrid reaction 3 hours, be warming up to 70 ℃ of reactions 1.5 hours, obtain modified butadiene-styrene latex.
Step 3: the powdered of modified styrene butadiene rubber
This latex is put into 20 liters of gel grooves, thin up is 10% to consolidating thing content, add the step 1 product high-molecular coating agent saponification aqueous solution 1200 grams again, at per minute is to mix 10 minutes under 200～300 commentaries on classics are stirred, spraying adding concentration is 5% calcium chloride solution 1200 grams, be warming up to 80 ℃, adding concentration is the antioxidant 264 of 10%20 grams and the sodium stearate dispersion liquid of 20 grams, the discharging of lowering the temperature then, washing after filtration,, dehydration, sieve, drying, obtain doing the modified styrene butadiene rubber powder that toughness reinforcing soft PVC goods are used.
Embodiment 4
Make the preparation method of toughness reinforcing soft PVC with the modified styrene butadiene rubber powder end, its processing step and condition are as follows:
Step 1: with embodiment 1
Step 2: the graft modification of styrene-butadiene rubber(SBR)
In 5 liters of reactors, add concentration and be 3.25 kilograms of 20% 1502 or 1500 styrene-butadiene latexes, stir the emulsion that adds 175 gram vinylbenzene, 70 gram vinyl cyanide, 105 gram butyl acrylates and 5.25 gram cumyl hydroperoxides down, after mixing 2 hours under 25～30 ℃, 10% aqueous solution that adds diethylamine tetraacethyl ferrisodium salt 1.05 grams and rongalite 2.1 grams again, hybrid reaction 3 hours, be warming up to 70 ℃ of reactions 1 hour, obtain modified butadiene-styrene latex.
Step 3: the powdered of modification fourth rubber
Modified butadiene-styrene latex is put into 20 liters of gel grooves, thin up is 8% to consolidating thing content, add the step 1 product high-molecular coating agent saponification aqueous solution 1200 grams again, at per minute is to mix 10 minutes under 200～300 commentaries on classics are stirred, spraying adding concentration is 5% calcium chloride solution 1200 grams, be warming up to 80 ℃, adding concentration is the antioxidant 264 of 10%20 grams and the sodium stearate dispersion liquid of 20 grams, slaking 10～20 minutes, the discharging of lowering the temperature then, after filtration, washing, dehydration is sieved, drying promptly obtains a kind of modified styrene butadiene rubber powder that toughness reinforcing soft PVC goods are used of doing.
Embodiment 5
Step 1: the preparation of high-molecular coating agent and embodiment 1 are together.
Step 2: precrosslink reaction
In 5 liters of reactors, add concentration and be 3.25 kilograms of 20% 1502 or 1500 styrene-butadiene latexes, stir the emulsion that adds 7 gram cumyl hydroperoxides down, be warming up to 70～80 ℃ of reactions 4 hours, obtain gel content greater than 65% precrosslink styrene-butadiene latex.
Step 3: styrene-butadiene latex graft reaction
When the precrosslink styrene-butadiene latex is cooled to 30 ℃, add 262.5 gram vinylbenzene, 87.5 gram vinyl cyanide and 5.25 gram cumyl hydroperoxide emulsifying mixture liquid, mixed 2 hours down at 25～30 ℃, 10% aqueous solution that adds diethylamine tetraacethyl ferrisodium salt 1.05 grams, rongalite 2.1 grams, hybrid reaction 3 hours, be warming up to 70 ℃ of reactions 1 hour, obtain modified butadiene-styrene latex.Be warming up to 80 ℃, adding concentration is 5% above-mentioned high-molecular coating agent 800 grams, and concentration is the antioxidant 264s of 10%20 grams and the sodium stearate dispersion liquids of 20 grams, mixes 15 minutes.
Step 4: the continuous powdered technology of modification fourth rubber
The device of powdered technology is made up of collection surface, ripening tank and storagetank continuously.The above-mentioned modified butadiene-styrene latex that is added with coating by a certain percentage continuously pump and spray continuously by a certain percentage by the collection surface top simultaneously that to add concentration be 5% calcium chloride solution to collection surface.Obtain fine particle cohesion modified powder styrene-butadiene rubber(SBR) suspension, through ripening tank, storagetank, again through centrifuge dehydration, wash, sieve, drying, promptly obtain the modified powder styrene-butadiene rubber(SBR) of whole particle diameters less than 0.45mm.
The precrosslink degree of latex depends on the consumption of linking agent, and the precrosslink degree of latex has tangible influence to the resistance to impact shock of modified product toughening PVC, and the result is as shown in table 1.The embodiment of the invention has all been used best crosslinking degree.
Modified styrene butadiene rubber is a nucleocapsid structure, examines to be rubber, plays the effect that absorbs energy, stops crack growth in toughness reinforcing blend; And shell is a graft copolymer, monomer form determined its with by the consistency of toughness reinforcing PVC, when the grafting layer with by toughness reinforcing PVC consistency when better, every better performances of blend.The size of nuclear and the composition of shell are as shown in table 2 to the influence of the resistance to impact shock of toughening PVC.Present embodiment is selected preferable cooperation for use.Embodiment 5 has narrated continuous cohesion powdered technology, and this technological equipment investment is bigger, but has improved usage ratio of equipment, to realizing that suitability for industrialized production is more favourable.The product particle diameter that continuous cohesion powdered technology obtains is littler, is suitable for the production process of production requirement small particle size powder.The relation of coating consumption and modified rubber powder particle diameter is as shown in table 3, and promptly many modified rubber powders particle diameter is thin more more for the coating consumption.
Table 1
| Dosage of crosslinking agent (in rubber weight) | 0 0.7 1.0 2 4 |
| Notched Izod impact strength (KJ/m 2) | 73 90 100 95 93 |
Table 2
Table 3
| Powder diameter distribution (%) | The coating consumption of per 100 weight part modified styrene butadiene rubbers (by the dry measure of multipolymer) |
| 2 3 4 5 6 7 | |
| ＞2mm ＜2mm ＜0.9mm ＜0.45mm ＜0.35mm | 65 45 2 1 0 0 36 55 98 99 100 100 10 45 97 98 99 100 3 37 65 85 97 98 1 16 31 43 84 92 |
Claims (3)
1. make the preparation method of toughness reinforcing rigid polyvinyl chloride, it is characterized in that its processing step and condition are as follows with modified styrene butadiene rubber powder:
Step 1: the preparation of high-molecular coating agent
(1) preparation of solution
By vinylbenzene: MALEIC ANHYDRIDE: the weight ratio of benzoyl peroxide is 100～110: the ratio that 94.2: 0.971～1.457 batching drops into toluene or toluene and hexanaphthene is in 1: 1～2 the mixed solvent, is mixed with 10～20% solution;
(2) copolyreaction
Be warming up to 60～80 ℃, reacted 2～3 hours, underpressure distillation after the solvent that adds all steams, obtains M
n=4～60,000 multipolymer;
(3) saponification
By multipolymer: the weight ratio of water is to add entry at 5: 93, and under whipped state, the sodium hydroxide or the potassium hydroxide of acid anhydrides equivalent in adding and the multipolymer, 70～80 ℃ of following saponification 2～4 hours, being coated with-4 glasss of viscosity is 15～25 seconds, pH value be 9～13 milky white to little yellow multipolymer saponification liquor, be coating;
Step 2: precrosslink reaction
Select 1502 or 1500 general SBR emulsions for use, add cumyl hydroperoxide, be warming up to 70～80 ℃ of reactions 2～5 hours, obtain gel content greater than 65% precrosslinked rubber latex by dried glue weight 0.7～2%;
Step 3: the graft modification of styrene-butadiene latex
Add vinylbenzene, vinyl cyanide and cumyl hydroperoxide at the prepared gel content of step 2 in greater than 65% precrosslinked rubber latex, its weight ratio is dried glue: vinylbenzene: vinyl cyanide: cumyl hydroperoxide=60～80: 30～15: 10～5: 0.6～0.30; Pre-swelling is 2～4 hours under 25～30 ℃, be that benchmark adds diethylamine tetraacethyl ferrisodium salt and rongalite again with the cumyl hydroperoxide, its weight ratio is 1: 0.1～0.3: 0.2～0.6, reacted 2～4 hours down at 25～30 ℃, be warmed up to 70～80 ℃ of reactions 1～3 hour, promptly obtain the graft modification styrene-butadiene latex;
Step 4: the powdered of modified styrene butadiene rubber
Under whipped state, to temperature is the deionized water that adds 1.5～2 times of its weight in 70～80 ℃ the modified butadiene-styrene latex, the high-molecular coating agent that adds the step 1 gained of pressing modified styrene butadiene rubber amount 2～6% again, add at last and press the calcium chloride of modified styrene butadiene rubber amount 2～6%, obtain micelle suspensoid by the crosslinked coating cohesion of coating, add anti-aging agent, stearic acid again, slaking 10～20 minutes, with this micelle suspensoid filter, wash, dewater, sieve, drying, promptly obtain toughness reinforcing rigid polyvinyl chloride modified styrene butadiene rubber powder.
2. make the preparation method of toughness reinforcing soft PVC, it is characterized in that its processing step and condition are as follows with modified styrene butadiene rubber powder:
Step 1: the preparation of high-molecular coating agent
(1) preparation of solution
By vinylbenzene: MALEIC ANHYDRIDE: the weight ratio of benzoyl peroxide is 100～110: the ratio that 94.2: 0.971～1.457 batching drops into toluene or toluene and hexanaphthene is in 1: 1～2 the mixed solvent, is mixed with 10～20% solution;
(2) copolyreaction
Be warming up to 60～80 ℃, reacted 2～3 hours, underpressure distillation after the solvent that adds all steams, obtains M
n=4～60,000 multipolymer;
(3) saponification
By multipolymer: the weight ratio of water is to add entry at 5: 93, and under whipped state, the sodium hydroxide or the potassium hydroxide of acid anhydrides equivalent in adding and the multipolymer, 70～80 ℃ of following saponification 2～4 hours, being coated with-4 glasss of viscosity is 15～25 seconds, pH value be 9～13 milky white to little yellow multipolymer saponification liquor, be coating;
Step 2: the graft modification of styrene-butadiene latex
In styrene-butadiene latex, add vinylbenzene without precrosslink, vinyl cyanide, butyl acrylate and cumyl hydroperoxide, its weight ratio is: by the non-crosslinked styrene-butadiene latex of dried glue: vinylbenzene: vinyl cyanide: Butyl acrylate: cumyl hydroperoxide=60～80: 20～15: 10～5: 10～0: 0.6～0.4; Pre-swelling is 2～4 hours under 25～30 ℃, be that benchmark adds diethylamine tetraacethyl ferrisodium salt and rongalite again with the cumyl hydroperoxide, its weight ratio is 1: 0.1～0.3: 0.2～0.6, reacted 2～4 hours down at 25～30 ℃, be warmed up to 70～80 ℃ of reactions 1～3 hour, promptly obtain the graft modification styrene-butadiene latex;
Step 3: the powdered of modified styrene butadiene rubber
Under whipped state, to temperature is the deionized water that adds 1.5～2 times of its weight in 70～80 ℃ the modified butadiene-styrene latex, the high-molecular coating agent that adds the step 1 gained of pressing modified styrene butadiene rubber amount 2～6% again, add at last and press the calcium chloride of modified styrene butadiene rubber amount 2～6%, obtain micelle suspensoid by the crosslinked coating cohesion of coating, add anti-aging agent, stearic acid again, slaking 10～20 minutes, with this micelle suspensoid filter, wash, dewater, sieve, drying, promptly obtain doing toughness reinforcing soft PVC modified styrene butadiene rubber powder.
3. the preparation method who makes the toughening polyvinyl chloride modified styrene butadiene rubber powder according to claim 12, the powdered step that it is characterized in that its modified styrene butadiene rubber adopts cohesion powdered method continuously, promptly except that calcium chloride, all the other components are disposable feeding intake after graft modification is finished all.
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| CN97111343A CN1052987C (en) | 1997-05-24 | 1997-05-24 | Method for preparing modified styrene butadiene rubber powder used as toughness-increased agent for poly vinyl chloride |
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| CN101921440B (en) * | 2009-06-16 | 2013-01-02 | 中国石油化工股份有限公司 | Method for improving ageing whiteness of toughening type PVC (Polyvinyl Chloride) resin |
| CN102952301B (en) * | 2011-08-19 | 2014-10-15 | 中国石油天然气股份有限公司 | Preparation method of oil resistant enhanced styrene-butadiene rubber polymer particles |
| CN104448446B (en) * | 2013-09-18 | 2016-08-17 | 中国石油天然气股份有限公司 | A kind of preparation method of environmental-protection flame-retardant powder styrene butadiene rubber |
| CN103819773A (en) * | 2014-02-28 | 2014-05-28 | 苏州瑞邦塑胶有限公司 | Improved TPV formula |
| CN108976446B (en) * | 2017-05-31 | 2021-04-13 | 中国石油化工股份有限公司 | Preparation method of powdered styrene butadiene rubber |
| CN107746448B (en) * | 2017-12-01 | 2020-03-17 | 山东东临新材料股份有限公司 | Preparation method of weather-resistant toughening agent for PVC transparent product |
| CN109929259B (en) * | 2019-04-17 | 2021-06-04 | 山东显元化工研究院有限公司 | SBR (styrene butadiene rubber) asphalt modifier and preparation method thereof |
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| JPS578431A (en) * | 1980-06-19 | 1982-01-16 | Mitsubishi Heavy Ind Ltd | Leakage detector for pipe joint |
| US5223577A (en) * | 1990-06-01 | 1993-06-29 | Basf Aktiengesellschaft | Abs molding materials |
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- 1997-05-24 CN CN97111343A patent/CN1052987C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS578431A (en) * | 1980-06-19 | 1982-01-16 | Mitsubishi Heavy Ind Ltd | Leakage detector for pipe joint |
| US5223577A (en) * | 1990-06-01 | 1993-06-29 | Basf Aktiengesellschaft | Abs molding materials |
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