CN107474192A - The production method of unsaturated acid anhydride Suspension Graft chlorinated polyethylene rubber - Google Patents
The production method of unsaturated acid anhydride Suspension Graft chlorinated polyethylene rubber Download PDFInfo
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- CN107474192A CN107474192A CN201710945601.3A CN201710945601A CN107474192A CN 107474192 A CN107474192 A CN 107474192A CN 201710945601 A CN201710945601 A CN 201710945601A CN 107474192 A CN107474192 A CN 107474192A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
- C08F255/023—On to modified polymers, e.g. chlorinated polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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Abstract
The production method of unsaturated acid anhydride Suspension Graft chlorinated polyethylene rubber, it is specifically：Deionized water, inorganic dispersant, surfactant are sequentially added in reaction vessel, is stirring evenly and then adding into haloflex and unsaturated carboxylic acid anhydrides；60 DEG C of stirrings；Sweller is added dropwise；It is warming up to 85 97 DEG C and adds free agent initiator progress aqueous-phase suspending graft reaction；After reaction terminates, solid crude product is filtered to obtain, liquid portion is as the mother liquor recycled；Crude product is through dry that target product, the sweller cooled down when drying are incorporated to Recycling Mother Solution use.Product has excellent sulfuration process, physical and mechanical properties and compatibility.There is typical flat region during vulcanization processing, tensile strength reaches 17.0MPa, and elongation at break is up to 440%, and the excellent rotproofness with CSM, is provided simultaneously with higher intensity and low cost.Suitable for products such as auto parts machinery, acidproof/oil-resisting rubber hose, electric wire, sponge, seal, waterproof roll and flame retardant rubbers.
Description
Technical field
The present invention relates to a kind of production method of unsaturated acid anhydride Suspension Graft chlorinated polyethylene rubber, and in particular to a kind of
The aqueous-phase suspending grafting production method of rubber-type unsaturated acid anhydride graft CPE material.
Background technology
Haloflex（CPE）With excellent weather-proof, resistance to ozone, chemical-resistant resistance, heat-resistant aging and fire-retardant etc. one
Serial good characteristic, while its raw material sources is abundant, manufacturing process is simple, cost is cheap.Therefore, CPE and its product are wide
It is general to be applied in auto parts machinery, acidproof/oil-resisting rubber hose, electric wire, sponge, seal, waterproof roll and anti-flaming rubber product,
As the focus studied both at home and abroad.
But the bottleneck for hindering its large-scale application is compatibility/tack（It is with other materials and poor with property）And sulfuration process
Property is bad（There is no the flat phase）And intensity is not high, thus by modification and with etc. technology improve its performance and turn into and key ask
Topic.
1994, Sun Yun C et al. are disclosed " was modified CPE " to improve PVC impact property（US 5338803）,
It is grafting agent with unsaturation vinyl monomer, such as：Methyl methacrylate etc., it is initiator with organic peroxide, uses
Suspension polymerization is prepared for graft CPE.
2006, Zhao Dong disclosed " graft copolymer of chlorinated polyethylene-alkyl-acrylates and its preparation method and should
With "（ZL 200610001895.6）, it is that the alkyl-acrylates compound and 75 95% chlorination that will account for 5 25% are gathered
Ethene is put into reactor, and adds water and 0.1 2% surfactant, in a nitrogen atmosphere stirring be warming up to 70 90 (TC,
Kept for 0.5 2 hours, the radical initiator for then adding 0.1 2% triggers copolyreaction, and is stirred at 50 500 revs/min
Mix and reacted 35 hours under speed, obtain graft copolymer of chlorinated polyethylene-alkyl-acrylates.
2014, Chen Erfan disclosed " a kind of unsaturated acid anhydride graft CPE melt production method "（CN
104292391 A）, it is parent with haloflex, and unsaturated acid anhydride is grafted monomers, is prepared for connecing using melt production method
Branch modified chlorinated polyethylene.It successfully solves compatibility/tack of haloflex and sulfuration process is bad asks
Topic.But the shortcoming of Modification by Melt Grafting method is：1. fusion method is carried out at relatively high temperatures, make haloflex by hot old
Change and thermal degradation；Haloflex macromolecular is set to produce degraded 2. larger shearing force can be produced by having with screw extruder；It is 3. difficult
To realize large-scale industrial production.
What aforementioned production method obtained is only the product of CPE powder surface modifications, the purpose is to prepare PVC modifying agent,
Elastomeric material use can not be acted on.
The content of the invention
It is an object of the invention to provide a kind of production method of unsaturated acid anhydride Suspension Graft chlorinated polyethylene rubber.This
Invention makes chlorinated polyethylene grafting carboxylic acid by aqueous-phase suspending graft reaction, under relatively low manufacturing condition（85-97
℃）, the chlorinated polyethylene rubber material of the excellent graft modification of efficient production performance.Products obtained therefrom mechanical property is good, compatibility
（Tack）Well, sulfuration process is good.There is typical flat region during vulcanization processing, tensile strength reaches 17.0MPa, and fracture is stretched
Long rate is up to 440%, and the excellent rotproofness with CSM, is provided simultaneously with higher intensity and low cost.It is suitable
For products such as auto parts machinery, acidproof/oil-resisting rubber hose, electric wire, sponge, seal, waterproof roll and flame retardant rubbers.
The purpose of the present invention is achieved through the following technical solutions：
The production method of unsaturated acid anhydride Suspension Graft chlorinated polyethylene rubber, it is related to a kind of rubber-type unsaturated acid anhydride grafting chlorine
Change the aqueous-phase suspending grafting production method of polythene material：Deionized water, inorganic dispersant, table are sequentially added in reaction vessel
Face activating agent, it is stirring evenly and then adding into graft bases haloflex and unsaturated carboxylic acid anhydrides grafting agent；60 DEG C of stirrings, make chlorination
Polyethylene is dispersed in water in powdered；Sweller is slowly added dropwise, is swelled；Haloflex is increasingly becoming little particle
Afterwards, it is warming up to 85-97 DEG C DEG C and adds free agent initiator, carries out aqueous-phase suspending graft reaction；After reaction terminates, suction filtration is consolidated
Body crude product, the mother liquor that liquid portion effect recycles；Haloflex of the crude product through dry graft modification, back tender
The sweller to be cooled down in skill is incorporated in the mother liquor of recycling；The sweller is dimethylbenzene（DMB）Or itself and acetic acid second
Ester（EAc）Mixture.
The production method of described unsaturated acid anhydride Suspension Graft chlorinated polyethylene rubber, by haloflex, unsaturation
Carboxylic acid anhydrides and radical initiator are proportionally added into polymeric kettle reactor, make haloflex by aqueous-phase suspending graft reaction
Grafted carboxylic acid.
The production method of described unsaturated acid anhydride Suspension Graft chlorinated polyethylene rubber, the inorganic dispersant are：In vain
Carbon black or fine particle calcium carbonate or the two mixture or the two mixture with titanium dioxide.
The production method of described unsaturated acid anhydride Suspension Graft chlorinated polyethylene rubber, the surfactant are：It is poly-
Oxygen vinethene, neopelex, Sodium stearate/potassium.
The production method of described unsaturated acid anhydride Suspension Graft chlorinated polyethylene rubber, the unsaturated carboxylic acid anhydrides are：
Maleic anhydride（MA）, citraconic anhydride（CTA）, dimethyl maleate acid anhydride（DMMA）, aconitic anhydride（ACA）, phenyl maleic acid
Acid anhydride（PMA）, itaconic anhydride（ITA）, or phthalic anhydride（PA）.
The production method of described unsaturated acid anhydride Suspension Graft chlorinated polyethylene rubber, the radical initiator, its
It is characterized in：Dibenzoyl peroxide（BPO）, cumyl peroxide（DCP）, cyclohexanone peroxide（CYHPO）, t-butyl peroxy
Change hydrogen（TBHP）, azodiisobutyronitrile（AIBN）, ABVN（ABVN）.
The production method of described unsaturated acid anhydride Suspension Graft chlorinated polyethylene rubber, the mass fraction of each component are：
100 parts of haloflex, 350~600 parts of deionized water, 0.4~10 part of inorganic dispersant, 0.4~5 part of surfactant, no
2~20 parts of saturated carboxylic acid acid anhydride, 4~80 parts of sweller, 0.03~0.6 part of radical initiator.
The production method of described unsaturated acid anhydride Suspension Graft chlorinated polyethylene rubber, the Recycling Mother Solution uses, right
The consumption component of last time Suspension Graft is supplemented.
The production method of described unsaturated acid anhydride Suspension Graft chlorinated polyethylene rubber, recycle mother liquor Suspension Graft
Method is：After sweller, deionized water, inorganic dispersant, surfactant supplement have been carried out to the mother liquor after recovery, stirring is equal
The unsaturated carboxylic acid anhydrides grafting agent of graft bases haloflex and magnitude of recruitment is added after even；60 DEG C of stirrings, make haloflex
It is dispersed in water, is swelled in powdered；After haloflex is increasingly becoming little particle, 85-97 DEG C is warming up to, then press
The amount of initiator input initiator of suspension polymerization first, carries out aqueous-phase suspending graft reaction.
The production method of described unsaturated acid anhydride Suspension Graft chlorinated polyethylene rubber, recycle mother liquor Suspension Graft
During method, supplementing the method for reactive component is：
Sweller, the swelling dosage to be cooled down in drying process is subtracted by suspension polymerization inventory first and is added to
In mother liquor；
Deionized water, subtract the masterbatch of recovery by the mother liquor amount of suspension polymerization first and the swelling dosage of supplement adds；
Inorganic dispersant, added by the 90-95% of the inventory of suspension polymerization first；
Surfactant, added by the 45-50% of the inventory of suspension polymerization first；
Unsaturated carboxylic acid anhydrides grafting agent, added by the 75-85% of the inventory of suspension polymerization first.
Advantages of the present invention is with effect：
1）Chlorinated polyethylene grafting carboxylic acid is made by aqueous-phase suspending graft reaction, under relatively low manufacturing condition（85-97
℃）, the chlorinated polyethylene rubber material of the excellent graft modification of efficient production performance.It is mainly manifested in：Mechanical property is good, compatible
Property（Tack）Good and product sulfuration process is good.
2）Using white carbon and fine particle calcium carbonate as dispersant, reaction system is stable, cost is cheap.
3）Dimethylbenzene and ethyl acetate are used as sweller, low toxicity, low stain, and adjustable reaction temperature is at 85-97 DEG C
Between, normal pressure or micro-pressure safety production and production efficiency height.
4）Mother liquor in production can be recycled, no discharge.
5）Processing condition and method is easy to the advantages that heavy industrialization and steady quality.
Brief description of the drawings
Fig. 1 be haloflex and maleic anhydride under the effect of BPO radical initiators, aqueous-phase suspending grafting gathers for chlorination
The reaction mechanism of ethylene-maleic acid graft.
Fig. 2 is that aqueous-phase suspending is grafted MA modification CPE products（Upper curve）With non-grafted CPE（Lower curve）Fourier transform
Infrared spectrum（FTIR）.It is grafted MA-CPE：Grafting rate 2%.In 1734cm-1Locate multiple absworption peaks, be carbonyl C=O characteristic peak, demonstrate,prove
Bright grafting occurs.
Fig. 3 is the curing curve of MA graft modification CPE sizing materials.170 DEG C of curing temperature；It is grafted MA-CPE：Grafting rate 2%.
Fig. 4 is the curing curve of the CPE sizing materials of unmodified grafting, without the flat phase.170 DEG C of curing temperature.
Curve c is the curing curve for the product for implementing 1 in Fig. 5；Curve b is that the vulcanization for the product for not using sweller is bent
Line, without the flat phase；Curve a is the curing curve for the product that hexamethylene is sweller, without the flat phase.
Embodiment
Below in conjunction with the accompanying drawings, the production method of unsaturated acid anhydride Suspension Graft chlorinated polyethylene rubber of the present invention is made in detail
Explanation.Illustration is used for the method and core concept for understanding the present invention, it is impossible to assert that the embodiment of the present invention only limits
In this, also should not be taken as being limitation of the present invention.To those skilled in the art, structure of the present invention is not being departed from
On the premise of think of, some simple deduction or replace are carried out, should be considered as belonging to protection scope of the present invention.
Present invention relates particularly to a kind of aqueous-phase suspending of rubber-type unsaturated acid anhydride graft CPE material to be grafted life
Production method.Reactions steps are：Deionized water, inorganic dispersant, surfactant are sequentially added in reaction vessel, is stirred
Graft bases haloflex and unsaturated carboxylic acid anhydrides grafting agent are added afterwards；60 DEG C of stirrings, make haloflex in powdered equal
It is even to be dispersed in water；Sweller is slowly added dropwise, is swelled；After haloflex is increasingly becoming little particle, 85-97 DEG C is warming up to
Free agent initiator is added, carries out aqueous-phase suspending graft reaction；After reaction terminates, suction filtration obtains solid crude product, liquid portion
Act on the mother liquor recycled；Haloflex of the crude product through dry graft modification, cool down in drying process molten
Swollen dose is incorporated in the mother liquor of recycling；The sweller is dimethylbenzene（DMB）Or itself and ethyl acetate（EAc）Mixture.
Haloflex, unsaturated carboxylic acid anhydrides and radical initiator are proportionally added into polymeric kettle reactor by the present invention
In, chlorinated polyethylene grafting carboxylic acid is made by aqueous-phase suspending graft reaction.
Inorganic dispersant is in the present invention：White carbon or fine particle calcium carbonate, or the mixture of white carbon and fine particle calcium carbonate, or it is white carbon, light
The mixture of calcium and titanium dioxide.
Surfactant is in the present invention：APEO, neopelex, Sodium stearate/potassium.
Unsaturated carboxylic acid anhydrides are：Maleic anhydride（MA）, citraconic anhydride（CTA）, dimethyl maleate acid anhydride（DMMA）, crow
Head acid anhydrides（ACA）, phenylmaleic anhydride（PMA）, itaconic anhydride（ITA）, or phthalic anhydride（PA）.
Radical initiator is：Dibenzoyl peroxide（BPO）, cumyl peroxide（DCP）, cyclohexanone peroxide
（CYHPO）, TBHP（TBHP）, azodiisobutyronitrile（AIBN）, ABVN（ABVN）.
The mass fraction of above-mentioned each component is：100 parts of haloflex, 350~600 parts of deionized water, inorganic dispersant
0.4~10 part, 0.4~5 part of surfactant, 2~20 parts of unsaturated carboxylic acid anhydrides, 4~80 parts of sweller, radical initiator
0.03~0.6 part.
Recycling Mother Solution of the present invention uses, and the consumption component to last time Suspension Graft supplements.
After product is purified, after parking 10h, grafting rate is tested.
Then, the auxiliary agents such as modified haloflex, carbon black, operation oil, age resistor are added sequentially to banburying in proportion
After being mixed in machine, bottom sheet, is made performance test sample on a mill.Determine its sulfuration process, mechanical property.
Grafting rate determines：
Grafting samples are put into reactor, 50 times 145 DEG C of reflux extraction 24h of dimethylbenzene is added, it is fully swelled, with except
Unreacted grafted monomers and possible maleic anhydride condensate are removed, then 80 DEG C are put into vacuum drying chamber drying 10h, obtain pure
The chlorinated polyethylene grafting thing of change.
Note：The grafting rate of other unsaturated acid anhydrides determines with reference to the method, mole matter of unsaturated acid anhydride corresponding to replacing
Amount calculates.
The accurate grafting samples 0.2g for weighing oneself purifying, is put into conical flask, adds 50ml dimethylbenzene, 145 DEG C are heated back
Flow lh to being swelled, while hot when instill excessive NaOH- ethanol 0.lmol/L standard liquids, then drip into a few drop phenolphthalein indicators extremely
Solution takes on a red color, and reheats 10min, excessive alkali HCI- isopropanol standard liquids（0.lmol/L）It is counter drop to it is colourless untill,
And blank test is done, the calculation formula of grafting rate is as follows：
……….（1）
In formula：V1To titrate the volume of the added ethanol solutions of NaOH mono-；
V2To titrate the volume of the consumed aqueous isopropanols of HCI mono-；
C1For the molar concentration of the ethanol solutions of NaOH mono-；
C2For the molar concentration of the aqueous isopropanols of HCI mono-；
W is the quality of the purifying graft accurately weighed；
M is the molal weight of maleic anhydride；
The ethanol standard liquids of NaOH mono- are 0.1mol/L；
The isopropanol standard liquids of HCI mono- are 0.1mol/L, prepare and demarcate by GB/T264-1983.
Circulating mother liquor application method：
After graft reaction, the liquid for filtering the reaction system got off is collected, and prepares the liquid for being graft-polymerized again
Mutually it is continuing with.But the consumption component of upper batch suspension polymerization need to be supplemented, i.e., be fed intake by suspension polymerization first
Than being supplemented in order.
Supplement specific method：
1. sweller, the swelling dosage to be cooled down in drying process is subtracted by suspension polymerization inventory first and is added to
In mother liquor.
2. deionized water, the masterbatch of recovery and the swelling dosage of supplement are subtracted by the mother liquor amount of suspension polymerization first
Add.
3. inorganic dispersant, added by the 90-95% of the inventory of suspension polymerization first.
4. surfactant, added by the 45-50% of the inventory of suspension polymerization first.
5. unsaturated carboxylic acid anhydrides grafting agent, added by the 75-85% of the inventory of suspension polymerization first.
Use the suspension polymerization method of circulating mother liquor：
After sweller, deionized water, inorganic dispersant, surfactant supplement have been carried out to the mother liquor after recovery, stir
The unsaturated carboxylic acid anhydrides grafting agent of graft bases haloflex and magnitude of recruitment is added afterwards；60 DEG C of stirrings, make the haloflex be in
It is powdered to be dispersed in water, it is swelled；After haloflex is increasingly becoming little particle, 85-97 DEG C is warming up to, then by head
The amount of initiator input initiator of secondary suspension polymerization, carries out aqueous-phase suspending graft reaction.
The preparation of elastomeric compound：
The auxiliary agents such as modified haloflex, carbon black, operation oil, age resistor are added sequentially to mix in banbury in proportion
Afterwards, bottom sheet on a mill, performance test sample is made.Determine its sulfuration process, mechanical property etc..
Performance test：
The Nexus 470 class FTIR analyzers samples produced with thermoelectricity Buddhist nun's high-tensile strength company of the U.S. carry out composition sign.
With vulcanization of rubber analyzer GT-M2000-A（High Speed Rail Testing Instruments Co., Ltd）Test grafting samples and non-grafted
The sulfuration process of sample；
Tensile strength and elongation at break are tested according to GB/T528-2009, in RGL-30A types（The auspicious lattice Limited Liability in Shenzhen is public
Department）Cupping machine carries out tension test, rate of extension 500mm/min to sample.
Embodiment 1
The mass parts of deionized water 400,2 parts of inorganic dispersant white carbon, surfactant 12 are sequentially added in reaction vessel
2 parts of sodium alkyl benzene sulfonate, it is stirring evenly and then adding into 100 parts of graft bases haloflex and grafting agent maleic anhydride（MA）15
Part；60 DEG C of stirrings, make haloflex be dispersed in powdered in water；Sweller dimethylbenzene is slowly added dropwise（DMB）60 parts,
It is swelled；After haloflex is increasingly becoming little particle, it is warming up to 91 DEG C and adds free agent initiator dibenzoyl peroxide
（BPO）0.45 part, carry out aqueous-phase suspending graft reaction 3 hours；After reaction terminates, suction filtration obtains solid crude product, liquid portion
Act on the mother liquor recycled；Haloflex of the crude product through dry graft modification.After purification of samples parks 10h, test
Grafting rate is 2.0%.
By modified haloflex after purification and carbon black, operate the auxiliary agents such as oil, age resistor be added sequentially in proportion it is close
After being mixed in mill, bottom sheet on a mill, the vulcanizate sample of obtained performance test.Determine its sulfuration process, mechanics
Performance.
Product structure characterizes the curve seen above in Fig. 2, and from curve, it can be seen that, the CPE of grafting exists than non-grafted CPE
1734cm-1Locate multiple absworption peaks, this is carbonyl C=O characteristic peak, and because product is by after purification, therefore can prove
Maleic anhydride has successfully been grafted on CPE.
Curing curve is shown in Fig. 3 curves, and the obvious flat phase occurs in curing curve；Tensile strength is 20.5MPa, and fracture is stretched
Long rate is up to 471%, hardness Shao A72.
Comparative example 1
With the CPE of non-grafted modification, by the vulcanizate sample that non-grafted CPE is prepared described in embodiment 1.Determine sulfuration process
Property, mechanical property.
Curing curve is shown in Fig. 4 curves, does not occur the flat phase；Tensile strength is 8.0MPa, and elongation at break is up to 401.7%, firmly
Spend Shao A69.
Comparative example 2
Sweller is not used, by preparing unsaturated acid anhydride Suspension Graft haloflex sample described in embodiment 1.Test grafting
Rate is 0.3%.The curing curve of test sample, see Fig. 5 curve b, do not occur the flat phase.
Comparative example 3
Hexamethylene is used as sweller, 71 DEG C of reaction temperature, aqueous-phase suspending graft reaction 8 hours, is prepared by described in embodiment 1
Unsaturated acid anhydride Suspension Graft haloflex sample.It is 0.6% to test grafting rate.The curing curve of test sample, see Fig. 5 songs
Line a, do not occur the flat phase.
Embodiment 2
By preparation graft modification haloflex sample described in embodiment 1：
The mass parts of deionized water 350,0.4 part of dispersant white carbon, 5 parts of surfactant polyoxyethylene ether, grafting agent neighbour benzene two
Formic anhydride（PA）2 parts, sweller dimethylbenzene（DMB）4 parts；85 DEG C of reaction temperature, initiator cumyl peroxide（DCP）0.03
Part.Aqueous-phase suspending graft reaction 5 hours；It is 0.45% to test grafting rate.
Reached by the vulcanizate sample that grafting CPE is prepared described in embodiment 1, tensile strength 18.5MPa, elongation at break
459%, hardness Shao A65.
Embodiment 3
By preparation graft modification haloflex sample described in embodiment 1：
4 parts of the mass parts of deionized water 600,6 parts of dispersant white carbon and fine particle calcium carbonate, 0.4 part of surfactant polyoxyethylene ether, grafting
Agent dimethyl maleate acid anhydride（DMMA）15 parts, sweller dimethylbenzene（DMB）60 parts and ethyl acetate（EAc）20 parts；Reaction
85 DEG C of temperature, initiator cyclohexanone peroxide（CYHPO）0.6 part.Aqueous-phase suspending graft reaction 6 hours；Testing grafting rate is
3.05%。
Reached by the vulcanizate sample that grafting CPE is prepared described in embodiment 1, tensile strength 18.7MPa, elongation at break
464%, hardness Shao A70.
Embodiment 4
By preparation graft modification haloflex sample described in embodiment 1：
The mass parts of deionized water 450,2 parts of 5 parts+fine particle calcium carbonate of dispersant white carbon, 3 parts+titanium dioxide, surfactant Sodium stearate
3.4 parts, grafting agent citraconic anhydride（CTA）20 parts, sweller dimethylbenzene（DMB）30 parts and ethyl acetate（EAc）30 parts；Reaction temperature
85 DEG C of degree, initiator TBHP（TBHP）0.5 part.Aqueous-phase suspending graft reaction 6 hours；Testing grafting rate is
3.45%。
Reached by the vulcanizate sample that grafting CPE is prepared described in embodiment 1, tensile strength 19.5MPa, elongation at break
471%, hardness Shao A73.
Embodiment 5
By preparation graft modification haloflex sample described in embodiment 1：
The mass parts of deionized water 550,4 parts of dispersant white carbon, 4.1 parts of surfactant potassium stearate, grafting agent aconitic anhydride
（ACA）18 parts, sweller dimethylbenzene（DMB）70 parts；97 DEG C of reaction temperature, initiator azodiisobutyronitrile（AIBN）0.4 part.Water
Phase Suspension Graft reacts 3 hours；It is 3.0% to test grafting rate.
Reached by the vulcanizate sample that grafting CPE is prepared described in embodiment 1, tensile strength 19.0MPa, elongation at break
481%, hardness Shao A75.
Embodiment 6
By preparation graft modification haloflex sample described in embodiment 1：
The mass parts of deionized water 500,10 parts of dispersant fine particle calcium carbonate, 5.0 parts of surfactant sodium dodecyl base benzene sulfonic acid sodium salt, grafting agent benzene
Base maleic anhydride（PMA）20 parts, sweller dimethylbenzene（DMB）50 parts and ethyl acetate（EAc）20 parts；85 DEG C of reaction temperature, draws
Send out agent ABVN（ABVN）0.6 part.Aqueous-phase suspending graft reaction 4 hours；It is 2.8% to test grafting rate.
Reached by the vulcanizate sample that grafting CPE is prepared described in embodiment 1, tensile strength 17.7MPa, elongation at break
470%, hardness Shao A72.
Embodiment 7
By preparation graft modification haloflex sample described in embodiment 1：
The mass parts of deionized water 430,5 parts of dispersant fine particle calcium carbonate, 0.4 part of surfactant polyoxyethylene ether, grafting agent itaconic anhydride
（ITA）16 parts, sweller dimethylbenzene（DMB）4 parts；93 DEG C of reaction temperature, initiator dibenzoyl peroxide（BPO）0.6 part.Water
Phase Suspension Graft reacts 3 hours；It is 1.7% to test grafting rate.
Reached by the vulcanizate sample that grafting CPE is prepared described in embodiment 1, tensile strength 17.7MPa, elongation at break
440%, hardness Shao A65.
Comparative example 4
Methacrylic acid is used as grafting agent, 71 DEG C of reaction temperature, by preparing unsaturated acids Suspension Graft chlorine described in embodiment 1
Change polyethylene specimen.It is 1.9% to test grafting rate.Tensile strength is 15.1MPa, and elongation at break is up to 400%, hardness Shao A62.
Embodiment 8
On the basis of implementing 1 component compatibility.Filtered in implementing 1 and obtain 341 parts of mother liquor, when crude product is dried, cool down the liquid of recovery
35 parts of body-sweller.
That is, 341 parts of the mother liquor of recovery of embodiment 1 and 59 parts of deionized water, the nothing of supplement are sequentially added in reaction vessel
1.9 parts of machine dispersant white carbon, 1 part of surfactant sodium dodecyl base benzene sulfonic acid sodium salt, are stirring evenly and then adding into graft bases chlorination
100 parts of polyethylene and grafting agent maleic anhydride（MA）12.75 parts；60 DEG C of stirrings, make haloflex in powdered dispersed
In water；35 parts of the sweller of cooling recovery and the dimethylbenzene of supplement is slowly added dropwise（DMB）25 parts, it is swelled；Chlorinated polyethylene
After alkene is increasingly becoming little particle, it is warming up to 91 DEG C and adds free agent initiator dibenzoyl peroxide（BPO）0.45 part, enter water-filling
Phase Suspension Graft reacts 3 hours；After reaction terminates, suction filtration obtains solid crude product, the mother liquor that liquid portion effect recycles；
Haloflex of the crude product through dry graft modification.After purification of samples parks 10h, test grafting rate is 1.9%.
Reached by the vulcanizate sample that grafting CPE is prepared described in embodiment 1, tensile strength 20.0MPa, elongation at break
469%, hardness Shao A71.
Embodiment 9
On the basis of implementing 1 component compatibility.Filtered in 10th batch of circulating mother liquor aqueous-phase suspending graft reaction and obtain 339 parts of mother liquor,
When crude product is dried, 37 parts of liquid-sweller of recovery is cooled down.
By described in embodiment 8 graft modification haloflex sample is prepared using circulating mother liquor：
To 61 parts of the deionized water of circulating mother liquor supplement, 1.9 parts of inorganic dispersant white carbon, surfactant sodium dodecyl base benzene sulphur
Sour 1.2 parts of sodium, maleic anhydride（MA）11.25 parts, the dimethylbenzene of supplement（DMB）23 parts.
Aqueous-phase suspending graft reaction 3 hours；It is 1.9% to test grafting rate.
Reached by the vulcanizate sample that grafting CPE is prepared described in embodiment 1, tensile strength 19.9MPa, elongation at break
468%, hardness Shao A72.
The performance of sample in comparing embodiment and comparative example, it can be seen that：
Sulfuration process of the graft modification CM products of the present invention than non-grafted CM samples is obviously improved, and is occurred typical
The flat phase（Fig. 3 is compared with Fig. 4 and Fig. 5）.
The graft modification CM products of the present invention double the above than the tensile strength of non-grafted CM samples, extension at break
Rate and firmness change are little.
Meanwhile the manufacturing cost of product/material of the present invention is low, steady quality.
On the other hand, the grafting used in the present invention is completed in molten condition, and the environment for reducing solvent working system is dirty
Dye.New growth engines is formed, the development of the theory related to material and product and production has reference function, improves high score
Sub- new material industry progress, has promoted the update of rubber-plastics material and product, has important Social benefit and economic benefit.
Claims (10)
1. the production method of unsaturated acid anhydride Suspension Graft chlorinated polyethylene rubber, it is related to a kind of rubber-type unsaturated acid anhydride grafting
The aqueous-phase suspending grafting production method of haloflex material, it is characterized in that：Deionized water, nothing are sequentially added in reaction vessel
Machine dispersant, surfactant, it is stirring evenly and then adding into graft bases haloflex and unsaturated carboxylic acid anhydrides grafting agent；60℃
Stirring, haloflex is set to be dispersed in powdered in water；Sweller is slowly added dropwise, is swelled；Haloflex by
After gradually turning into little particle, it is warming up to 85-97 DEG C DEG C and adds free agent initiator, carry out aqueous-phase suspending graft reaction；Reaction terminates
Afterwards, filter and obtain solid crude product, the mother liquor that liquid portion effect recycles；Chlorination of the crude product through dry graft modification
Polyethylene, the sweller to cool down in drying process are incorporated in the mother liquor of recycling;
The sweller is dimethylbenzene（DMB）Or itself and ethyl acetate（EAc）Mixture.
2. according to the production method of the unsaturated acid anhydride Suspension Graft chlorinated polyethylene rubber described in claim 1, it is characterized in that：
Haloflex, unsaturated carboxylic acid anhydrides and radical initiator are proportionally added into polymeric kettle reactor, pass through aqueous-phase suspending
Graft reaction makes chlorinated polyethylene grafting carboxylic acid.
3. according to the production method of the unsaturated acid anhydride Suspension Graft chlorinated polyethylene rubber described in claim 1, it is characterized in that：
The inorganic dispersant is：White carbon or fine particle calcium carbonate or the two mixture or the two mixture with titanium dioxide.
4. according to the production method of the unsaturated acid anhydride Suspension Graft chlorinated polyethylene rubber described in claim 1, it is characterized in that：
The surfactant is：APEO, neopelex, Sodium stearate/potassium.
5. according to the production method of the unsaturated acid anhydride Suspension Graft chlorinated polyethylene rubber described in claim 1, it is characterized in that：
The unsaturated carboxylic acid anhydrides are：Maleic anhydride（MA）, citraconic anhydride（CTA）, dimethyl maleate acid anhydride（DMMA）, aconitic acid
Acid anhydride（ACA）, phenylmaleic anhydride（PMA）, itaconic anhydride（ITA）, or phthalic anhydride（PA）.
6. according to the production method of the unsaturated acid anhydride Suspension Graft chlorinated polyethylene rubber described in claim 1, it is characterized in that：
The radical initiator, it is characterized in that：Dibenzoyl peroxide（BPO）, cumyl peroxide（DCP）, peroxidating hexamethylene
Ketone（CYHPO）, TBHP（TBHP）, azodiisobutyronitrile（AIBN）, ABVN（ABVN）.
7. according to the production method of the unsaturated acid anhydride Suspension Graft chlorinated polyethylene rubber described in claim 1-6, its feature
It is：The mass fraction of each component is：100 parts of haloflex, 350~600 parts of deionized water, 0.4 ~ 10 part of inorganic dispersant,
0.4~5 part of surfactant, 2~20 parts of unsaturated carboxylic acid anhydrides, 4~80 parts of sweller, 0.03~0.6 part of radical initiator.
8. according to the production method of the unsaturated acid anhydride Suspension Graft chlorinated polyethylene rubber described in claim 1, it is characterized in that：
The Recycling Mother Solution uses, and the consumption component to last time Suspension Graft supplements.
9. according to the production method of the unsaturated acid anhydride Suspension Graft chlorinated polyethylene rubber described in claim 1, it is characterized in that：
Recycling mother liquor Suspension Graft method is：Sweller, deionized water, inorganic dispersant, table have been carried out to the mother liquor after recovery
After the activating agent supplement of face, the unsaturated carboxylic acid anhydrides grafting agent of graft bases haloflex and magnitude of recruitment is stirring evenly and then adding into；
60 DEG C of stirrings, make haloflex be dispersed in powdered in water, are swelled；Haloflex is increasingly becoming little particle
Afterwards, 85-97 DEG C is warming up to, then initiator is put into by the amount of initiator of suspension polymerization first, carries out aqueous-phase suspending grafting
Reaction.
10. according to the production method of the unsaturated acid anhydride Suspension Graft chlorinated polyethylene rubber described in claim 9, its feature
It is：When recycling mother liquor Suspension Graft method, supplementing the method for reactive component is：
Sweller, the swelling dosage to be cooled down in drying process is subtracted by suspension polymerization inventory first and adds to mother
In liquid；
Deionized water, subtract the masterbatch of recovery by the mother liquor amount of suspension polymerization first and the swelling dosage of supplement adds；
Inorganic dispersant, added by the 90-95% of the inventory of suspension polymerization first；
Surfactant, added by the 45-50% of the inventory of suspension polymerization first；
Unsaturated carboxylic acid anhydrides grafting agent, added by the 75-85% of the inventory of suspension polymerization first.
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| Title |
|---|
| 潘祖仁等著: "《塑料工业手册：聚氯乙烯》", 31 August 1999, 化学工业出版社 * |
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