CN1386793A - Modifier for increasing impact resistance of polyvinyl chloride - Google Patents
Modifier for increasing impact resistance of polyvinyl chloride Download PDFInfo
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- CN1386793A CN1386793A CN 02117956 CN02117956A CN1386793A CN 1386793 A CN1386793 A CN 1386793A CN 02117956 CN02117956 CN 02117956 CN 02117956 A CN02117956 A CN 02117956A CN 1386793 A CN1386793 A CN 1386793A
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Abstract
An anti-impact modifier for polyvinyl chloride contains core (96-100 wt.%) and surficial plastic phase (0-4 wt.%). Said core is the homopolymer of butyl acrylate (BA) or the copolymer of butyl acrylate and triglycol acrylate. Said surficial plastic phase is the methyl methylacrylate. It can improve the antiimpact strength of PVC by 21 times and its toughness.
Description
Technical field:
The invention belongs to a kind of properties-correcting agent that improves impact resistance of polyvinyl chloride and preparation method thereof.
Background technology:
Polyvinyl chloride (PVC) is the very big class engineering plastics of excellent property, low price, output, and its shortcoming is that shock resistance is poor, and matter is crisp.For overcoming this shortcoming, enlarge the commercial use of polyvinyl chloride (PVC), study on the modification to polyvinyl chloride has carried out decades, and obtained tangible achievement, really make polyvinyl chloride become a kind of more general engineering plastics, brought into play vital role in industry, building, field such as civilian.
The properties-correcting agent that polyvinyl chloride is carried out impact modification generally is based on the lower elastomerics of second-order transition temperature, form core/shell structure with the good top layer of body material consistency in the grafting again, especially the acrylate based copolymer of releasing in nineteen fifties with U.S. Rohm and Haas company (ACR) is representative, has many anti-impact modifiers such as ABS, MBS, EVA, CPE to appear on the market thereupon again and obtains widespread use.
Chinese patent 95117702.8 KP Lodz stock thatch cards (Rozkusxka) and JE Wei Er (weier) disclose a kind of core/shell structure PVC anti-impact modifier, basic composition is of this core/shell structure PVC anti-impact modifier: its nuclear phase accounts for the weight 75～95% of total grade of part, is by the senior C of vinylformic acid in weight 60～80% butyl acrylates and weight 20～40% compositing ranges
8～C
12The multipolymer of alkyl monomer constitutes, and shell mainly is by weight 50% methacrylic acid C at least
1～C
4Alkyl ester constitutes.It belongs to most typical core/shell structure material.In this patent, the inventor has protected the PVC anti-impact modifier of its nuclear phase component from 75～95 (weight parts), i.e. nuclear phase component a series of products from low to high.When the blending amount that provides at embodiment was 8 parts, the part intermingling material ruptured in the toughness mode.
Summary of the invention:
An object of the present invention is to provide a kind of properties-correcting agent that improves impact resistance of polyvinyl chloride; Another object of the present invention provides a kind of preparation method who improves the properties-correcting agent of impact resistance of polyvinyl chloride.
Toughner provided by the invention is nuclear with lightly crosslinked butyl polyacrylate microballoon rubber elastomer particle, a small amount of and the good polymethylmethacrylate (PMMA) of PVC consistency in the grafting, form shell or star structure side chain, as the increase-volume segment, be beneficial to the dispersion of toughner particle in polyvinyl chloride resin.This anti-impact modifier can cause in large quantities in impact process and stop crazing, thereby absorbs a large amount of striking energys and reach and improve the flexible purpose.The present invention has synthesized rubber and plastic than being not quite similar with traditional core/shell structure particle, has high nuclear phase component anti-impact modifier, improves the homodisperse degree of toughner particle in PVC.
Anti-impact modifier nuclear of the present invention is the homopolymer of butyl acrylate (BA) or butyl acrylate and vinylformic acid triethyleneglycol ester multipolymer, account for 96～100% of particle total weight percent, top layer plastics phase component is the Polymerization of Methyl thing, account for 0～4% of particle total weight percent, preparation process is as follows:
1) preparation of seed emulsion:
Remove ionized water and be 2～4 times of weight ratio of nuclear monomer, add emulsifying agent sodium laurylsulfonate (SLS) 1.5～2.2g/L water, adding water soluble starter Potassium Persulphate consumption is 0.1～1% of nuclear monomer weight percent, nitrogen protection, stir, in 60 ℃-85 ℃ polymerization 2-5 hour, seed emulsion;
2) seed propagation process:
Pre-emulsion: by weight percentage, nuclear monomer: deionized water: emulsifying agent: initiator: linking agent: grafting agent=100: 10～20: 0.2～0.5: 0.1～1.0: 0～1.5: 0～1.0; Nuclear monomer is a butyl acrylate, and emulsifying agent is sodium laurylsulfonate (SLS), and initiator is hydrogen phosphide cumene (CHP), and linking agent is the vinylformic acid triethyleneglycol ester, and grafting agent is an allyl acrylate, uses mulser emulsification, and it is standby that the gained pre-emulsion is deposited bottle;
Seed increases: deionized water is 2～4 times of nuclear monomer weight ratio; add seed emulsion and account for 2～20% of nuclear monomer weight percent; reductive agent sodium formaldehyde sulphoxylate (Diao Bai piece) is 0.1～2.0% of a nuclear monomer weight percent; nitrogen protection; stir; dripping pre-emulsion to particle diameter in 60 ℃-85 ℃ is 90-220nm, drips off the back and continues reaction 1-3 hour.
3) shell graft polymerization:
Shell grafted monomer methyl methacrylate consumption and butyl acrylate are 0-4: 96-100 by weight percentage, add uncle's lauryl mercaptan of 0-0.1%; Initiator hydrogen phosphide cumene consumption is the 1-2.0% of shell monomers weight percent, and nitrogen protection is stirred, and in 60 ℃-85 ℃ dropping shell monomers, continues reaction 1-3 hour, filters, condenses, is drying to obtain anti-impact modifier.
Resistance to impact shock can reach 1200J/m when the anti-impact modifier consumption of the present invention's preparation was 10 parts, and batten is a ductile rupture, and shock strength improves 21 times than pure PVC material, and toughening effect is splendid.
Embodiment is as follows:
Embodiment 1:
The preparation of seed emulsion: in the 1000ml there-necked flask of agitator, reflux condensate device is housed, feed nitrogen protection, 60 ℃ of constant temperature; add deionized water 400g; 0.20g sodium laurylsulfonate, 20g butyl acrylate, 0.20g Potassium Persulfate; stir; dropping is by the 200gBA monomer, 60g deionized water, the pre-emulsion that 0.9g SLS emulsifying agent is formed; polymerization 2 hours gets seed emulsion.
The preparation pre-emulsion: claim BA monomer 300g, remove ionized water 30g, SLS emulsifying agent 0.6g, CHP initiator are 0.3g, and three vinylformic acid triethyleneglycol ester 2.0g carry out emulsification with mulser and get pre-emulsion.
Seed increases: with the 400g deionized water, 0.20g sodium laurylsulfonate adds in the there-necked flask, stir, 60 ℃ of logical nitrogen deoxygenations down, add 0.40g Diao Bai piece, the 10g seed emulsion drips pre-emulsion, adds 0.20g Diao Bai piece and 0.20g sodium laurylsulfonate, continue reaction 2 hours, begin to drip 8g shell reaction monomers methyl methacrylate and 0.10g hydrogen phosphide cumene mixture, add Potassium Persulfate 0.20g, continue reaction 1 hour, the cooling emulsion, filter, this particle dia is 220 nanometers, obtains the nucleocapsid weight ratio and be 96/4 anti-impact modifier.
Take by weighing 100 parts of polyvinylchlorides, CaCO
33 parts, 3 parts of calcium stearates, 1 part of lead sulfate tribasic, 1 part of ACR I processing aid, 3 parts of titanium dioxides add 8 parts of anti-impact modifiers, and thorough mixing makes it homodisperse, in 180 ℃ times mixing 5 minutes, obtains toughening modifying PVC sheet material on double roll mill.The sheet material that refining is good is superimposed together to be placed on and is pressed into the thick print of 3.0mm on the vulcanizing press under 180 ℃, with AJU-22 type Apparatus for Impacting at low-temp test cantilever beam impact strength, probe temperature is 22 ℃, press similarity condition, changing the anti-impact modifier add-on is 10 parts, the cantilever beam impact strength value of test toughening modifying PVC batten, concrete outcome sees Table 1.
Embodiment 2
The preparation of seed emulsion: in the 1000ml there-necked flask of agitator, reflux condensate device is housed, feed nitrogen protection, 60 ℃ of constant temperature; add deionized water 400g; 0.20g sodium laurylsulfonate, 20g butyl acrylate, 0.20g Potassium Persulfate; stir; dropping is by the 200gBA monomer, 60g deionized water, the pre-emulsion that 0.9g SLS emulsifying agent is formed; polymerization 2 hours gets seed emulsion.
The preparation pre-emulsion: claim BA monomer 300g, remove ionized water 45g, SLS emulsifying agent 1.5g, CHP initiator are 3.0g, and grafting agent allyl methacrylate(AMA) 3.0g carries out emulsification with mulser and gets pre-emulsion.
Seed increases: with the 500g deionized water, 0.20g sodium laurylsulfonate adds in the there-necked flask, stir, 60 ℃ of logical nitrogen deoxygenations down, add 0.40g Diao Bai piece, the 10g seed emulsion drips pre-emulsion again, adds 0.20g Diao Bai piece and 0.20g sodium laurylsulfonate, continue reaction 2 hours, begin to drip 6g shell reaction monomers methyl methacrylate and 0.10g hydrogen phosphide cumene and uncle's 0.01g lauryl mercaptan mixture, add Potassium Persulfate 0.20g, continue reaction 1 hour, the cooling emulsion, filter, this particle dia is 220 nanometers, obtains the nucleocapsid weight ratio and be 97/3 anti-impact modifier.
Take by weighing 100 parts of polyvinylchlorides, CaCO
33 parts, 3 parts of calcium stearates, 1 part of lead sulfate tribasic, 1 part of ACR I processing aid, 3 parts of titanium dioxides add 8 parts of anti-impact modifiers, carry out thorough mixing and make it homodisperse, in 180 ℃ times mixing 5 minutes, obtain toughening modifying PVC sheet material on double roll mill.The sheet material that refining is good is superimposed together to be placed on and is pressed into the thick print of 3.0mm on the vulcanizing press under 180 ℃, with AJU-22 type Apparatus for Impacting at low-temp test cantilever beam impact strength, probe temperature is 22 ℃, press similarity condition, changing the anti-impact modifier add-on is 10 parts, the cantilever beam impact strength value of test toughening modifying PVC batten, concrete outcome sees Table 1.
Embodiment 3
The preparation of seed emulsion: in the 1000ml there-necked flask of agitator, reflux condensate device is housed, feed nitrogen protection, 60 ℃ of constant temperature; add deionized water 400g; 0.20g sodium laurylsulfonate, 20g butyl acrylate, 0.20g Potassium Persulfate; stir; dropping is by the 200gBA monomer, 60g deionized water, the pre-emulsion that 0.9g SLS emulsifying agent is formed; polymerization 2 hours gets seed emulsion.
The preparation pre-emulsion: claim BA monomer 300g, remove ionized water 30g, SLS emulsifying agent 1.5g, CHP initiator are 0.90g, and three vinylformic acid triethyleneglycol ester 4.5g carry out emulsification with mulser and get pre-emulsion.
Seed increases: with the 600g deionized water, 0.20g sodium laurylsulfonate adds in the there-necked flask, stir, 60 ℃ of logical nitrogen deoxygenations down, add 0.40g Diao Bai piece, the 10g seed emulsion drips pre-emulsion again, adds 0.20g Diao Bai piece and 0.20g sodium laurylsulfonate, continue reaction 2 hours, begin to drip 2g shell reaction monomers methyl methacrylate and 0.10g hydrogen phosphide cumene and uncle's 0.01g lauryl mercaptan mixture, add Potassium Persulfate 0.20g, continue reaction 1 hour, the cooling emulsion, filter, this particle dia is 220 nanometers, obtains the nucleocapsid weight ratio and be 99/1 anti-impact modifier.
Take by weighing 100 parts of polyvinylchlorides, CaCO
33 parts, 3 parts of calcium stearates, 1 part of lead sulfate tribasic, 1 part of ACR I processing aid, 3 parts of titanium dioxides add 8 parts of anti-impact modifiers, carry out thorough mixing and make it homodisperse, in 180 ℃ times mixing 5 minutes, obtain toughening modifying PVC sheet material on double roll mill.The sheet material that refining is good is superimposed together to be placed on and is pressed into the thick print of 3.0mm on the vulcanizing press under 180 ℃, with AJU-22 type Apparatus for Impacting at low-temp test cantilever beam impact strength, probe temperature is 22 ℃, press similarity condition, changing the anti-impact modifier add-on is 10 parts, the cantilever beam impact strength value of test toughening modifying PVC batten, concrete outcome sees Table 1.
Embodiment 4
The preparation pre-emulsion: claim BA monomer 300g, remove ionized water 60g, SLS emulsifying agent 1.5g, CHP initiator are 0.90g, and three vinylformic acid triethyleneglycol ester 4.5g carry out emulsification with mulser and get pre-emulsion.
The production of hybrid seeds and seed increase: agitator is being housed; in the 1000ml there-necked flask of reflux condensate device; feed nitrogen protection; 60 ℃ of constant temperature; add deionized water 400g; 0.20g sodium laurylsulfonate; 0.10g Potassium Persulfate, the 20g Butyl Acrylate Monomer reacts after 1 hour; drip pre-emulsion; add 0.20g Diao Bai piece and 0.20g sodium laurylsulfonate, drip 8g shell reaction monomers methyl methacrylate and 0.10g hydrogen phosphide cumene mixture, continue reaction 1 hour; add Potassium Persulfate 0.20g; continue reaction 3 hours, the cooling emulsion is filtered; this particle dia is 220 nanometers, obtains the nucleocapsid weight ratio and be 96/4 anti-impact modifier.
Take by weighing 100 parts of polyvinylchlorides, CaCO
33 parts, 3 parts of calcium stearates, 1 part of lead sulfate tribasic, 1 part of ACR I processing aid, 3 parts of titanium dioxides add 8 parts of anti-impact modifiers, carry out thorough mixing and make it homodisperse, in 180 ℃ times mixing 5 minutes, obtain toughening modifying PVC sheet material on double roll mill.The sheet material that refining is good is superimposed together to be placed on and is pressed into the thick print of 3.0mm on the vulcanizing press under 180 ℃, with AJU-22 type Apparatus for Impacting at low-temp test cantilever beam impact strength, probe temperature is 22 ℃, press similarity condition, changing the anti-impact modifier add-on is 10 parts, the cantilever beam impact strength value of test toughening modifying PVC batten, concrete outcome sees Table 1.
Embodiment 5
The preparation pre-emulsion: claim BA monomer 300g, remove ionized water 60g, SLS emulsifying agent 1.5g, CHP initiator are 0.90g, and grafting agent allyl acrylate 1.0g carries out emulsification with mulser and gets pre-emulsion.
The production of hybrid seeds and seed increase: agitator is being housed; in the 1000ml there-necked flask of reflux condensate device; feed nitrogen protection; 60 ℃ of constant temperature; add deionized water 600g; 0.20g sodium laurylsulfonate; 0.10g Potassium Persulfate; the 20g Butyl Acrylate Monomer; maintenance system reaction 1 hour; drip pre-emulsion, add 0.20g Diao Bai piece and 0.20g sodium laurylsulfonate, continue reaction 2 hours; drip 6g shell reaction monomers methyl methacrylate and 0.10g hydrogen phosphide cumene mixture; continue reaction 1 hour, add Potassium Persulfate 0.20g, continue reaction 3 hours; the cooling emulsion; filter, this particle dia is 220 nanometers, obtains the nucleocapsid weight ratio and be 97/3 anti-impact modifier.
Take by weighing 100 parts of polyvinylchlorides, CaCO
33 parts, 3 parts of calcium stearates, 1 part of lead sulfate tribasic, 1 part of ACR I processing aid, 3 parts of titanium dioxides add 8 parts of anti-impact modifiers, carry out thorough mixing and make it homodisperse, in 180 ℃ times mixing 5 minutes, obtain toughening modifying PVC sheet material on double roll mill.The sheet material that refining is good is superimposed together to be placed on and is pressed into the thick print of 3.0mm on the vulcanizing press under 180 ℃, with AJU-22 type Apparatus for Impacting at low-temp test cantilever beam impact strength, probe temperature is 22 ℃, press similarity condition, changing the anti-impact modifier add-on is 10 parts, the cantilever beam impact strength value of test toughening modifying PVC batten, concrete outcome sees Table 1.
Embodiment 6
The preparation pre-emulsion: claim BA monomer 300g, remove ionized water 30g, SLS emulsifying agent 1.5g, CHP initiator are 0.90g, and three vinylformic acid triethyleneglycol ester 4.5g carry out emulsification with mulser and get pre-emulsion.
The production of hybrid seeds and seed increase: agitator is being housed; in the 1000ml there-necked flask of reflux condensate device; feed nitrogen protection; 60 ℃ of constant temperature; add deionized water 500g; 0.20g sodium laurylsulfonate; 0.10g Potassium Persulfate; add the 20g Butyl Acrylate Monomer; react and began to drip pre-emulsion in 1 hour; add 0.20g Diao Bai piece and 0.20g sodium laurylsulfonate; continue reaction 2 hours; begin to drip 2g shell reaction monomers methyl methacrylate and 0.10g hydrogen phosphide cumene mixture, add Potassium Persulfate 0.20g, continue reaction 3 hours; the cooling emulsion; filter, this particle dia is 220 nanometers, obtains the nucleocapsid weight ratio and be 99/1 anti-impact modifier.
Take by weighing 100 parts of polyvinylchlorides, CaCO
33 parts, 3 parts of calcium stearates, 1 part of lead sulfate tribasic, 1 part of ACR I processing aid, 3 parts of titanium dioxides add 8 parts of anti-impact modifiers, carry out thorough mixing and make it homodisperse, in 180 ℃ times mixing 5 minutes, obtain toughening modifying PVC sheet material on double roll mill.The sheet material that refining is good is superimposed together to be placed on and is pressed into the thick print of 3.0mm on the vulcanizing press under 180 ℃, with AJU-22 type Apparatus for Impacting at low-temp test cantilever beam impact strength, probe temperature is 22 ℃, press similarity condition, changing the anti-impact modifier add-on is 10 parts, the cantilever beam impact strength value of test toughening modifying PVC batten, concrete outcome sees Table 1.
Embodiment 7
The preparation of seed emulsion: in the 1000ml there-necked flask of agitator, reflux condensate device is housed, feed nitrogen protection, 60 ℃ of constant temperature; add deionized water 400g; 0.20g sodium laurylsulfonate, 20g butyl acrylate, 0.20g Potassium Persulfate; stir; dropping is by the 200gBA monomer, 60g deionized water, the pre-emulsion that 0.9g SLS emulsifying agent is formed; polymerization 2 hours gets seed emulsion.
The preparation pre-emulsion: claim BA monomer 300g, remove ionized water 45g, SLS emulsifying agent 1.5g, CHP initiator are 3.0g, and grafting agent allyl acrylate 1.5g carries out emulsification with mulser and gets pre-emulsion.
Seed increases: with the 400g deionized water, 0.20g sodium laurylsulfonate adds in the there-necked flask, stir, 60 ℃ of logical nitrogen deoxygenations down, add 0.40g Diao Bai piece, the 100g seed emulsion drips pre-emulsion again, adds 0.20g Diao Bai piece and 0.20g sodium laurylsulfonate, continue reaction 2 hours, begin to drip 8g shell reaction monomers methyl methacrylate and 0.10g hydrogen phosphide cumene and uncle's 0.01g lauryl mercaptan mixture, add Potassium Persulfate 0.20g, continue reaction 1 hour, the cooling emulsion, filter, this particle dia is 90 nanometers, obtains the nucleocapsid weight ratio and be 96/4 anti-impact modifier.
Take by weighing 100 parts of polyvinylchlorides, CaCO
33 parts, 3 parts of calcium stearates, 1 part of lead sulfate tribasic, 1 part of ACR I processing aid, 3 parts of titanium dioxides add 8 parts of anti-impact modifiers, carry out thorough mixing and make it homodisperse, in 180 ℃ times mixing 5 minutes, obtain toughening modifying PVC sheet material on double roll mill.The sheet material that refining is good is superimposed together to be placed on and is pressed into the thick print of 3.0mm on the vulcanizing press under 180 ℃, with AJU-22 type Apparatus for Impacting at low-temp test cantilever beam impact strength, probe temperature is 22 ℃, press similarity condition, changing the anti-impact modifier add-on is 10 parts, the cantilever beam impact strength value of test toughening modifying PVC batten, concrete outcome sees Table 1.
Embodiment 8
The preparation of seed emulsion: in the 1000ml there-necked flask of agitator, reflux condensate device is housed, feed nitrogen protection, 60 ℃ of constant temperature; add deionized water 400g; 0.20g sodium laurylsulfonate, 20g butyl acrylate, 0.20g Potassium Persulfate; stir; dropping is by the 200gBA monomer, 60g deionized water, the pre-emulsion that 0.9g SLS emulsifying agent is formed; polymerization 2 hours gets seed emulsion.
The preparation pre-emulsion: claim BA monomer 300g, remove ionized water 60g, SLS emulsifying agent 1.5g, CHP initiator are 0.90g, and three vinylformic acid triethyleneglycol ester 4.5g carry out emulsification with mulser and get pre-emulsion.
Seed increases: with the 600g deionized water, 0.60g sodium laurylsulfonate adds in the there-necked flask, stir, 60 ℃ of logical nitrogen deoxygenations down, add 0.40g Diao Bai piece, the 100g seed emulsion drips pre-emulsion again, adds 0.20g Diao Bai piece and 0.20g sodium laurylsulfonate, continue reaction 2 hours, begin to drip 2g shell reaction monomers methyl methacrylate and 0.10g hydrogen phosphide cumene and uncle's 0.01g lauryl mercaptan mixture, add Potassium Persulfate 0.20g, continue reaction 1 hour, the cooling emulsion, filter, this particle dia is 90 nanometers, obtains the nucleocapsid weight ratio and be 99/1 anti-impact modifier.
Take by weighing 100 parts of polyvinylchlorides, CaCO
33 parts, 3 parts of calcium stearates, 1 part of lead sulfate tribasic, 1 part of ACR I processing aid, 3 parts of titanium dioxides add 8 parts of anti-impact modifiers.Carry out thorough mixing and make it homodisperse, on double roll mill,, obtain toughening modifying PVC sheet material in 180 ℃ times mixing 5 minutes.The sheet material that refining is good is superimposed together to be placed on and is pressed into the thick print of 3.0mm on the vulcanizing press under 180 ℃, with AJU-22 type Apparatus for Impacting at low-temp test cantilever beam impact strength, probe temperature is 22 ℃, press similarity condition, changing the anti-impact modifier add-on is 10 parts, the cantilever beam impact strength value of test toughening modifying PVC batten, concrete outcome sees Table 1.
Embodiment 9
The preparation of seed emulsion: in the 1000ml there-necked flask of agitator, reflux condensate device is housed, feed nitrogen protection, 60 ℃ of constant temperature; add deionized water 400g; 0.20g sodium laurylsulfonate, 20g butyl acrylate, 0.20g Potassium Persulfate; stir; dropping is by the 200gBA monomer, 60g deionized water, the pre-emulsion that 0.9g SLS emulsifying agent is formed; polymerization 2 hours gets seed emulsion.
The preparation pre-emulsion: claim BA monomer 300g, remove ionized water 30g, SLS emulsifying agent 0.6g, CHP initiator are 0.3g, three vinylformic acid triethyleneglycol ester 1.0g, and grafting agent allyl acrylate 1.5g carries out emulsification with mulser and gets pre-emulsion.
Seed increases: with the 200g deionized water, 0.20g sodium laurylsulfonate adds in the there-necked flask, stir, 60 ℃ of logical nitrogen deoxygenations down, add 0.40g Diao Bai piece, the 50g seed emulsion drips pre-emulsion again, adds 0.20g Diao Bai piece and 0.20g sodium laurylsulfonate, continue reaction 2 hours, begin to drip 8g shell reaction monomers methyl methacrylate and 0.10g hydrogen phosphide cumene and uncle's 0.01g lauryl mercaptan mixture, add Potassium Persulfate 0.20g, continue reaction 1 hour, the cooling emulsion, filter, this particle dia is 150 nanometers, obtains the nucleocapsid weight ratio and be 96/4 anti-impact modifier.
Take by weighing 100 parts of polyvinylchlorides, CaCO
33 parts, 3 parts of calcium stearates, 1 part of lead sulfate tribasic, 1 part of ACR I processing aid, 3 parts of titanium dioxides add 8 parts of anti-impact modifiers, carry out thorough mixing and make it homodisperse, in 180 ℃ times mixing 5 minutes, obtain toughening modifying PVC sheet material on double roll mill.The sheet material that refining is good is superimposed together to be placed on and is pressed into the thick print of 3.0mm on the vulcanizing press under 180 ℃, with AJU-22 type Apparatus for Impacting at low-temp test cantilever beam impact strength, probe temperature is 22 ℃, press similarity condition, changing the anti-impact modifier add-on is 10 parts, the cantilever beam impact strength value of test toughening modifying PVC batten, concrete outcome sees Table 1.
Embodiment 10
The preparation pre-emulsion: claim BA monomer 300g, remove ionized water 60g, SLS emulsifying agent 1.5g, CHP initiator are 0.90g, carry out emulsification with mulser and get pre-emulsion.
The production of hybrid seeds and seed increase: in the 1000ml there-necked flask of agitator, reflux condensate device is housed; nitrogen protection; 60 ℃ of constant temperature; add deionized water 400g; 0.20g sodium laurylsulfonate, 0.10g Potassium Persulfate add the 20g Butyl Acrylate Monomer, react to begin to drip pre-emulsion in 1 hour; add 0.20g Diao Bai piece and 0.20g sodium laurylsulfonate, continue reaction 2 hours.The cooling emulsion is filtered, and this particle dia is the anti-impact modifier of 220 nanometers.
Take by weighing 100 parts of polyvinylchlorides, CaCO
33 parts, 3 parts of calcium stearates, 1 part of lead sulfate tribasic, 1 part of ACR I processing aid, 3 parts of titanium dioxides add 8 parts of anti-impact modifiers, carry out thorough mixing and make it homodisperse, in 180 ℃ times mixing 5 minutes, obtain toughening modifying PVC sheet material on double roll mill.The sheet material that refining is good is superimposed together to be placed on and is pressed into the thick print of 3.0mm on the vulcanizing press under 180 ℃, with AJU-22 type Apparatus for Impacting at low-temp test cantilever beam impact strength, probe temperature is 22 ℃, press similarity condition, changing the anti-impact modifier add-on is 10 parts, the cantilever beam impact strength value of test toughening modifying PVC batten, concrete outcome sees Table 1.
Embodiment 11
The preparation of seed emulsion: in the 1000ml there-necked flask of agitator, reflux condensate device is housed, feed nitrogen protection, 60 ℃ of constant temperature; add deionized water 400g; 0.20g sodium laurylsulfonate, 20g butyl acrylate, 0.20g Potassium Persulfate; stir; dropping is by the 200gBA monomer, 60g deionized water, the pre-emulsion that 0.9g SLS emulsifying agent is formed; polymerization 2 hours gets seed emulsion.
The preparation pre-emulsion: claim BA monomer 300g, remove ionized water 30g, SLS emulsifying agent 0.6g, CHP initiator are 0.3g, and three vinylformic acid triethyleneglycol ester 1.5g carry out emulsification with mulser and get pre-emulsion.
Seed increases: with the 600g deionized water, the 0.20g sodium laurylsulfonate adds in the there-necked flask, stirs, 60 ℃ of logical nitrogen deoxygenations down, add 0.40g Diao Bai piece, drip pre-emulsion after the 50g seed emulsion, add 0.20g Diao Bai piece and 0.20g sodium laurylsulfonate, continue reaction 1 hour.The cooling emulsion is filtered, and this particle dia is the anti-impact modifier of 150 nanometers.
Take by weighing 100 parts of polyvinylchlorides, CaCO
33 parts, 3 parts of calcium stearates, 1 part of lead sulfate tribasic, 1 part of ACR I processing aid, 3 parts of titanium dioxides add 8 parts of anti-impact modifiers, carry out thorough mixing and make it homodisperse, in 180 ℃ times mixing 5 minutes, obtain toughening modifying PVC sheet material on double roll mill.The sheet material that refining is good is superimposed together to be placed on and is pressed into the thick print of 3.0mm on the vulcanizing press under 180 ℃, with AJU-22 type Apparatus for Impacting at low-temp test cantilever beam impact strength, probe temperature is 22 ℃, press similarity condition, changing the anti-impact modifier add-on is 10 parts, the cantilever beam impact strength value of test toughening modifying PVC batten, concrete outcome sees Table 1.
Comparative example
Take by weighing 100 parts of polyvinylchlorides, CaCO
33 parts, 3 parts of calcium stearates, 1 part of lead sulfate tribasic, 1 part of ACR I processing aid, 3 parts of titanium dioxides do not add any toughner, carry out thorough mixing and make it homodisperse, in 180 ℃ times mixing 5 minutes, obtain toughening modifying PVC sheet material on double roll mill.The sheet material that refining is good is superimposed together to be placed on and is pressed into the thick print of 3.0mm on the vulcanizing press under 180 ℃, and with AJU-22 type Apparatus for Impacting at low-temp test cantilever beam impact strength, probe temperature is 22 ℃.
Pure polyvinyl chloride cantilever beam impact strength value is 53J/m under this condition, is brittle rupture.
Table 1 toughening modifying PVC sample impact value
Probe temperature notched Izod impact strength value (J/m)
Embodiment
(℃) 10 parts of modifier embodiment 1 22 470 982 embodiment 2 22 680 1200 embodiment 3 22 588 952 embodiment 4 22 569 900 embodiment 5 22 200 580 embodiment 6 22 580 880 embodiment 7 22 432 520 embodiment 8 22 310 420 embodiment 9 22 490 680 embodiment 10 22 380 960 embodiment 11 22 240 510 of 8 parts of modifier addings of adding
Claims (7)
1, a kind of properties-correcting agent that improves impact resistance of polyvinyl chloride, comprise rubber phase and plastics two kinds of weave constructions mutually, it is characterized in that properties-correcting agent nuclear is the homopolymer of butyl acrylate or butyl acrylate and vinylformic acid triethyleneglycol ester multipolymer, account for 96～100% of particle total weight percent, top layer plastics phase component is the Polymerization of Methyl thing, accounts for 0～4% of particle total weight percent.
2, a kind of preparation method who improves the properties-correcting agent of impact resistance of polyvinyl chloride is characterized in that preparation process is as follows:
1) preparation of seed emulsion:
Remove ionized water and be 2～4 times of weight ratio of nuclear monomer, add emulsifying agent sodium laurylsulfonate 1.5～2.2g/L water, adding the water soluble starter consumption is 0.1～1% of nuclear monomer weight percent, nitrogen protection, stir, in 60 ℃-85 ℃ polymerization 2-5 hour, seed emulsion;
2) seed propagation process:
Pre-emulsion: by weight percentage, nuclear monomer: deionized water: emulsifying agent: initiator: linking agent: grafting agent=100: 10～20: 0.2～0.5: 0.1～1.0: 0～1.5: 0～1.0; Nuclear monomer is a butyl acrylate, uses mulser emulsification, and it is standby that the gained pre-emulsion is deposited bottle;
Seed increases: deionized water is 2～4 times of nuclear monomer weight ratio, add seed emulsion and account for 2～20% of nuclear monomer weight percent, reductive agent is 0.1～2.0% of a nuclear monomer weight percent, nitrogen protection, stir, dripping pre-emulsion to particle diameter in 60 ℃-85 ℃ is 90-220nm, continues reaction 1-3 hour;
3) shell graft polymerization:
Shell grafted monomer methyl methacrylate consumption and butyl acrylate are 0-4: 96-100 by weight percentage, add uncle's lauryl mercaptan of 0-0.1%; Initiator hydrogen phosphide cumene consumption is the 1-2.0% of shell monomers weight percent, and nitrogen protection is stirred, and in 60 ℃-85 ℃ dropping shell monomers, continues reaction 1-3 hour, filters, condenses, is drying to obtain anti-impact modifier.
3, the properties-correcting agent of raising impact resistance of polyvinyl chloride as claimed in claim 2 is characterized in that water soluble starter is a Potassium Persulphate in the preparation of seed emulsion.
4, the properties-correcting agent of raising impact resistance of polyvinyl chloride as claimed in claim 2 is characterized in that nuclear monomer is a butyl acrylate in the seed propagation process.
5. the properties-correcting agent of raising impact resistance of polyvinyl chloride as claimed in claim 2, the emulsifying agent that it is characterized in that pre-emulsion in the seed propagation process is a sodium laurylsulfonate, initiator is a hydrogen phosphide cumene, and linking agent is the vinylformic acid triethyleneglycol ester, and grafting agent is an allyl acrylate.
6, the properties-correcting agent of raising impact resistance of polyvinyl chloride as claimed in claim 2 is characterized in that reductive agent is a sodium formaldehyde sulphoxylate in the seed propagation process.
7, the properties-correcting agent of raising impact resistance of polyvinyl chloride as claimed in claim 2 is characterized in that grafting agent is allyl methacrylate(AMA) or allyl acrylate.
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| CN 02117956 CN1266214C (en) | 2002-05-27 | 2002-05-27 | Modifier for increasing impact resistance of polyvinyl chloride |
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| CN 02117956 CN1266214C (en) | 2002-05-27 | 2002-05-27 | Modifier for increasing impact resistance of polyvinyl chloride |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101328234B (en) * | 2007-06-18 | 2010-09-29 | 山东瑞丰高分子材料股份有限公司 | Polychloroethylene composition for non-transparent foaming sheet for outdoor decoration |
| CN101418057B (en) * | 2007-10-23 | 2010-11-17 | 山东瑞丰高分子材料股份有限公司 | Rigid PVC resin auxiliary agent applied to plastic sliding door decorative door-plate |
| CN104119628A (en) * | 2013-04-26 | 2014-10-29 | 彭朕财 | Transparent PMMA (polymethyl methacrylate) particle powder toughening agent |
| CN104327216B (en) * | 2014-10-15 | 2017-02-08 | 山东世拓高分子材料股份有限公司 | Terpolymer used for hard polyvinyl chloride and preparation method thereof |
| CN108219085A (en) * | 2017-12-12 | 2018-06-29 | 常州市万昌化工有限公司 | A kind of preparation method of high impact-resistant water-resistant type epoxy resin toughener |
| CN108250515A (en) * | 2018-02-22 | 2018-07-06 | 高密浩翰木塑材料科技有限公司 | A kind of preparation of anti-impact modifier and the application in PVC matrix |
| CN108424495A (en) * | 2018-03-31 | 2018-08-21 | 长春工业大学 | A kind of preparation method of plasticizing polylactic acid nucleocapsid acrylate polymer |
| CN110628156A (en) * | 2018-06-23 | 2019-12-31 | 深圳市宝聚合塑料有限公司 | Composite polymerized acrylate rubber and preparation method thereof |
| CN112646334A (en) * | 2020-11-27 | 2021-04-13 | 宁波工程学院 | High-strength heat-resistant modified polylactic acid and preparation method thereof |
| CN117659543A (en) * | 2023-12-06 | 2024-03-08 | 广东中讯通讯设备实业有限公司 | High-strength plastic-steel composite PE cable protection pipe and preparation method thereof |
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- 2002-05-27 CN CN 02117956 patent/CN1266214C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101328234B (en) * | 2007-06-18 | 2010-09-29 | 山东瑞丰高分子材料股份有限公司 | Polychloroethylene composition for non-transparent foaming sheet for outdoor decoration |
| CN101418057B (en) * | 2007-10-23 | 2010-11-17 | 山东瑞丰高分子材料股份有限公司 | Rigid PVC resin auxiliary agent applied to plastic sliding door decorative door-plate |
| CN104119628A (en) * | 2013-04-26 | 2014-10-29 | 彭朕财 | Transparent PMMA (polymethyl methacrylate) particle powder toughening agent |
| CN104119628B (en) * | 2013-04-26 | 2017-06-16 | 彭朕财 | Transparent PMMA particle powders toughener |
| CN104327216B (en) * | 2014-10-15 | 2017-02-08 | 山东世拓高分子材料股份有限公司 | Terpolymer used for hard polyvinyl chloride and preparation method thereof |
| CN108219085A (en) * | 2017-12-12 | 2018-06-29 | 常州市万昌化工有限公司 | A kind of preparation method of high impact-resistant water-resistant type epoxy resin toughener |
| CN108250515A (en) * | 2018-02-22 | 2018-07-06 | 高密浩翰木塑材料科技有限公司 | A kind of preparation of anti-impact modifier and the application in PVC matrix |
| CN108424495A (en) * | 2018-03-31 | 2018-08-21 | 长春工业大学 | A kind of preparation method of plasticizing polylactic acid nucleocapsid acrylate polymer |
| CN110628156A (en) * | 2018-06-23 | 2019-12-31 | 深圳市宝聚合塑料有限公司 | Composite polymerized acrylate rubber and preparation method thereof |
| CN112646334A (en) * | 2020-11-27 | 2021-04-13 | 宁波工程学院 | High-strength heat-resistant modified polylactic acid and preparation method thereof |
| CN117659543A (en) * | 2023-12-06 | 2024-03-08 | 广东中讯通讯设备实业有限公司 | High-strength plastic-steel composite PE cable protection pipe and preparation method thereof |
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