CN1576311A - Polyvinyl chloride propenoic acid esters impact modifier - Google Patents
Polyvinyl chloride propenoic acid esters impact modifier Download PDFInfo
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Abstract
The acrylate impact modifier for polyvinyl chloride with excellent weather resistance, machinability and impact resistance is prepared via mixing acrylate core-shell grafting copolymer and machining assistant. The acrylate core-shell grafting copolymer has acrylate elastomer content as high as 80 %, vitrification point of control core part lower than -20 deg.c, vitrification point of shell part higher than 50 deg.c, emulsion number-average grain size of 150-500 nm, and raised impact strength of the impact modifier. The addition of the machining assistant improves the flowability and machining property of the impact modifier. In addition, the product contains no double bond and thus has excellent weather resistance.
Description
Technical field
The present invention relates to a kind of polyvinyl chloride acrylic ester impact-resisting modifier, specifically, relate to the polyvinyl chloride acrylic ester impact-resisting modifier of a kind of weathering resistance, shock resistance, excellent processability.
Background technology
In general, it is poor that polyvinyl chloride (PVC) RESINS shapes performance, must add processing aid, to improve its processing characteristics; The resistance to impact shock of the goods after polyvinyl chloride shapes is poor, and people have invented several different methods to improve the resistance to impact shock of polrvinyl chloride product.
One of them method is exactly to add the terpolymer of butadiene-styrene-methyl methacrylate, and just the MBS resin improves the shock strength of polrvinyl chloride product.Although but the resistance to impact shock of resulting goods was than higher after the MBS resin was processed with the mixture of PVC, weathering resistance is poor, and after outdoor application for some time, the resistance to impact shock of goods can descend rapidly.So the polyvinyl chloride of MBS modification can only be in indoor use.
The reason of MBS resin weathering resistance difference is because the UV resistant performance of main component polyhutadiene wherein is poor.In order to improve the weathering resistance of MBS, people have invented not double bond containing anti-impact modifier, acrylic ester impact-resisting modifier again.Acrylic ester impact-resisting modifier is the acrylate nucleoid-shell graft copolymer (special public clear 51-28117 communique) that obtains by monomeric mixtures such as grafting alkyl methacrylate, vinylbenzene, vinyl cyanide on lightly crosslinked acrylic ester elastomer.The nuclear of acrylate nucleoid-shell graft copolymer partly is acrylic ester elastomer.Have good weathering resistance with the impact-resistant modified polrvinyl chloride product of this acrylate nucleoid-shell graft copolymer, but resistance to impact shock is undesirable.
Nucleoid-the shell graft copolymer center partly is the content of acrylate elastomer in order to improve acrylate to improve the effective means of resistance to impact shock, content is high more good more, be preferably 100%, after but its content improves, the processibility of acrylate nucleoid-shell graft copolymer is relatively poor, powder fluidity is poor, can produce caking phenomenon when serious.Therefore the special public clear 58-4735 of Japanese Patent reports that the weight percent content of acrylic ester elastomer can not surpass 80% in acrylate nucleoid-shell graft copolymer impact modifier.
September 12 calendar year 2001, disclosed CN1312298A reported a kind of shock resisting polyvinyl chloride modifier, contained alkylmethacrylate class 4.5-45%, the higher alkyl methacrylate 0.5-5% of the alkylacrylate 50-95% of at least a rubber phase, at least two kinds of thermoplastic phases in its feed composition.Although this impact processing modifier can make the erosion-resisting characteristics of polyvinyl chloride (PVC) Compound make moderate progress, the inventor is through discovering that the effect of this impact processing modifier is still undesirable.To have reduced nuclear part be the content of acrylate elastomer to the graft copolymer shell in acrylate nucleoid-shell graft copolymer impact modifier, makes the shock resistance effect of goods reduce.Grafted alkyl methacrylate, vinylbenzene, vinyl cyanide are the polymkeric substance of main Cheng Yuan on the acrylic ester elastomer simultaneously, originally be effective polyvinyl chloride processing aid, can improve the processing characteristics of polyvinyl chloride widely, but in fact the processing characteristics of polyvinyl chloride (PVC) Compound and graft copolymer shell content are irrelevant, that is to say because of it to be grafted to former on the elastomerics thereby to have lost its processing characteristics.
Therefore, the processing characteristics and the shock resistance of the blend of being made by traditional acrylate nucleoid-shell graft copolymer impact modifier and polyvinyl chloride are all undesirable.
Summary of the invention
The present invention is for the problem of the processibility, shock resistance and the weathering resistance that solve traditional impact modifier of polyvinyl chloride, the weight percent content of acrylic ester elastomer in acrylate nucleoid-shell graft copolymer that overcomes traditional impact modifier surpasses that 80% o'clock powder fluidity is poor, the shortcoming of poor processability, proposed a kind of improved polyvinyl chloride acrylic ester impact-resisting modifier.
The polyvinyl chloride acrylic ester impact-resisting modifier of a kind of weathering resistance, shock resistance, excellent processability is made by following weight percentages: acrylate nucleoid-shell graft copolymer 65-97%, processing aid 3-35%.Described acrylate nucleoid-shell graft copolymer partly is made up of nuclear part and shell, and the nuclear part is an acrylic ester elastomer, and the weight percent content of acrylic ester elastomer is greater than 80%.The content of acrylic ester elastomer is high more, and shock resistance is high more.According to the needs of resistance to impact shock, the content of free adjustment acrylic ester elastomer.The weight percent content of acrylic ester elastomer is less than 80%, and then shock resistance descends.
The nuclear of described acrylate nucleoid-shell graft copolymer partly is to comprise the lightly crosslinked acrylic ester elastomer that the monomer mixture polymerization of alkyl acrylate obtains, and the preferred glass temperature is less than-20 ℃ acrylic ester elastomer.When the second-order transition temperature of acrylic ester elastomer was higher than-20 ℃, the shock resistance of the polrvinyl chloride product of being made by this properties-correcting agent descended.Described shell partly is to be the high molecular polymer of main component with the alkyl methacrylate, and the preferred glass temperature is greater than 50 ℃.The second-order transition temperature of shell part is high more, is difficult for the adhesion caking between the impact modifier particles more, needs the processing aid of adding few more.Less than 50 ℃, then the powder fluidity degradation of acrylic ester impact-resisting modifier needs to add more processing aid to improve its powder fluidity as shell second-order transition temperature partly.
The preferred 150-500nm of the number average bead diameter of emulsion particle in the latex of described acrylate nucleoid-shell graft copolymer.Number average bead diameter is during less than 150nm, and the shock resistance of impact modifier descends.
The preparation method of described acrylate nucleoid-shell graft copolymer is as follows:
(1) seed latex is synthetic: with the tensio-active agent of the radical initiator of the linking agent that contains two or more carbon-carbon double bonds of the water of 80-120 weight part, 40-60 parts by weight of acrylic alkyl ester, 0.01-3 weight part, 0.001-1 weight part, 0.1-2 weight part, join in the reactor, in nitrogen atmosphere, be warming up to 50-80 ℃, with 100-500 rev/min speed stirring reaction 6-10 hour, obtain the seed latex that number average bead diameter is 120-160nm;
(2) the acrylic ester elastomer emulsion is synthetic: with the water of 60-100 weight part, the seed latex that the step of 20-80 weight part (1) obtains, 0.3-1.5 the tensio-active agent of weight part joins in the reactor, in nitrogen atmosphere, be warming up to 50-80 ℃, under 100-500 rev/min speed agitation condition again with 80-100 parts by weight of acrylic alkyl ester, 0.01-5 the linking agent that contains two or more carbon-carbon double bonds of weight part and the radical initiator of 0.001-1 weight part are divided into 2-4 and criticize adding, each timed interval that adds is 1-3 hour, is incubated the emulsion that obtained containing acrylic ester elastomer in 3-5 hour then;
(3) acrylate nucleoid-shell graft copolymer is synthetic: the emulsion that contains 150-200 parts by weight of acrylic acid ester elastomer that step (2) is obtained, the water of 1-25 weight part, 0.01-0.5 the tensio-active agent of weight part, the alkyl methacrylate of 1-25 weight part, 0-2.5 the radical initiator of parts by weight of acrylic alkyl ester and 0.001-0.2 weight part joins in the reactor, under nitrogen atmosphere, be warming up to 50-80 ℃, with down reaction 3-5 hour of 100-500 rev/min speed agitation condition, obtaining the acrylate elastomer weight percent content is the emulsion of acrylate nucleoid-shell graft copolymer of 150-500nm greater than 80% number average bead diameter.
The second-order transition temperature of acrylic ester elastomer can be regulated by the content of acrylic ester monomer in elastomerics in change step (2) the elastomerics building-up process.When acrylic ester monomer content was high, second-order transition temperature was low, when acrylic ester monomer content hangs down, the second-order transition temperature height, when the acrylate weight percent content greater than 70% the time, second-order transition temperature is lower than-20 ℃.
The second-order transition temperature of the shell of nuclear-shell graft copolymer is regulated by the content that changes acrylic ester monomer in the shell in the building-up process of step (3) acrylate nucleoid-shell graft copolymer, when the weight percent content of acrylic ester monomer less than 30% the time, the second-order transition temperature of shell is greater than 50 ℃.
The particle diameter of emulsion particle can be regulated by the consumption that changes seed latex in step (2) the elastomerics building-up process, and the consumption of seed latex is few more, and the particle diameter of nuclear-shell graft copolymer emulsion particle is big more.
In the building-up process of step (3) acrylate nucleoid-shell graft copolymer, change the content of acrylic ester elastomer in acrylate nucleoid-shell graft copolymer by the consumption that changes acrylate elastomer.Improve the consumption of acrylate elastomer, the content of acrylic ester elastomer then increases in synthetic acrylate nucleoid-shell graft copolymer.Therefore as required, can freely regulate the content of acrylic ester elastomer in acrylate nucleoid-shell graft copolymer.At the alkyl methacrylate described in the building-up process can be one matter, also can be the mixture of multiple alkyl methacrylate.
In the described improved acrylic ester impact-resisting modifier of preparation, described processing aid is selected from following processing aid A, B, C, D, E, F, and they are made by following preparation method respectively:
(1) processing aid A: the alkyl methacrylate of the water of 50-70 weight part, 30-40 weight part, 0-20 parts by weight of acrylic alkyl ester, the tensio-active agent of 0.1-1 weight part, the radical initiator of 0.001-0.5 weight part are joined in the reactor, to be warming up to 50-80 ℃ under 50-500 rev/min the speed stirring, reacted 2-4 hour;
(2) processing aid B: the alpha-methyl styrene of the vinyl cyanide of the vinylbenzene of the water of 50-70 weight part, 20-25 weight part, 1-10 weight part, 0-10 weight part, 0-10 parts by weight of acrylic alkyl ester, the tensio-active agent of 0.1-1 weight part, the radical initiator of 0.001-0.5 weight part are joined in the reactor, to be warming up to 50-80 ℃ under 50-500 rev/min the speed stirring, reacted 2-4 hour;
(3) processing aid C:
The emulsion of described processing aid A and the emulsion mixing of described processing aid B are obtained, and wherein the weight percent content of processing aid A, B emulsion is: described processing aid A 0-100%, described processing aid B 0-100%;
(4) processing aid D: the chlorallylene of the vinyl cyanide of the vinylbenzene of the alkyl methacrylate of the water of 100 weight parts, 0-100 weight part, 0-30 parts by weight of acrylic alkyl ester, 0-85 weight part, 0-40 weight part, 0-20 weight part or glycidyl methacrylate, the tensio-active agent of 0.1-2 weight part, the radical initiator of 0.001-1 weight part are joined in the reactor, to be warming up to 50-80 ℃ under 100-500 rev/min the speed stirring, reacted 2-4 hour;
(5) processing aid E: join the monomer mixture of the emulsion of the emulsion of processing aid A and processing aid B in the reactor simultaneously, under stirring, 100-500 rev/min speed is warming up to 50-80 ℃, reaction obtained the emulsion of processing aid E in 2-4 hour, and wherein the weight percent content of the emulsion of processing aid A is that the weight percent content of monomer mixture of the emulsion of 0-100%, processing aid B is 0-100%;
(6) processing aid F: join the monomer mixture of the emulsion of the emulsion of processing aid B and processing aid A in the reactor simultaneously, under stirring, 100-500 rev/min speed is warming up to 50-80 ℃, reaction obtained the emulsion of processing aid F in 2-4 hour, and wherein the weight percent content of the emulsion of processing aid B is that the weight percent content of monomer mixture of the emulsion of 0-100%, processing aid A is 0-100%.
The described linking agent that contains two or more carbon-carbon double bonds is to contain two or more compounds that can carry out the carbon-carbon double bond of radical copolymerization with the alkyl-acrylates monomer, allyl methacrylate(AMA) for example, Vinylstyrene, Phthalic acid, diallyl ester, allyl acrylate, Ethylene glycol dimethacrylate, ethylene glycol diacrylate, Phthalic acid, diallyl ester, Viscoat 295, trimethylolpropane trimethacrylate, described radical initiator is a di-isopropylbenzene hydroperoxide, Potassium Persulphate, ammonium persulphate, Sodium Persulfate, tertbutyl peroxide, hydrogen phosphide cumene, described tensio-active agent are Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, sodium stearate, potassium stearate.
The carbonatoms of the alkyl of described alkyl acrylate is 2-8, for example vinylformic acid propyl diester, butyl acrylate cores, vinylformic acid amyl group ester, Isooctyl acrylate monomer, vinylformic acid heptyl ester.
The carbonatoms of the alkyl of described alkyl methacrylate is 1-8, methyl methacrylate for example, methacrylic acid propyl diester, methacrylic acid butyl ester, methacrylic acid amyl group ester, Isooctyl methacrylate, methacrylic heptyl heptylate.
Used radical initiator in the process of preparation acrylate nucleoid-shell graft copolymer and various processing aids, mechanism according to radical polymerization, if the water hardness of using is bigger, meetings such as the metal ion that contains hinder the carrying out of reaction, therefore will be according to used water hardness, Xiang Shuizhong adds complexing agents such as EDTA or its disodium salt with the calcium ion in the complexing water etc.If the water that uses is less as distilled water or hardness, then do not need to add these complexing agents.Also can in water, add simultaneously an amount of ferrous sulfate, rongalite carrying out as required with accelerated reaction.Ferrous sulfate, rongalite play the effect of catalyzer in polymerization process.
Described improved acrylic ester impact-resisting modifier is made by acrylate nucleoid-shell graft copolymer and processing aid blend.The mode of blend is not particularly limited, can adopt the mode of emulsion blending, also both can be dried to powder respectively after, adopt the mode of powder blend, drying mode can adopt and saltout, centrifugal, exsiccant mode, also can adopt spray-dired mode.For example adopt emulsion to mix the back, stirred 0.5-2 hour, carry out spraying drying then and obtain described improved acrylic ester impact-resisting modifier.Also can adopt the adding water-soluble inorganic salt, as adding calcium chloride, sodium-chlor, nitrocalcite, condense, centrifuge dehydration, drying obtain described improved acrylic ester impact-resisting modifier.
Impact modifier of the present invention is applied to the polyvinyl chloride (PVC) Compound goods, can make the polyvinyl chloride (PVC) Compound goods have excellent weathering resistance, shock resistance and processibility.The prescription of polyvinyl chloride (PVC) Compound is: major ingredient is the polyvinyl chloride and the 2-20 weight part acrylic ester impact-resisting modifier of the present invention of 80-98 weight part, and both parts by weight sums are 100; With 100 weight part major ingredients is that the auxiliary material that benchmark adds is the lime carbonate of 0-15 weight part, the titanium dioxide of 0-8 weight part, the thermo-stabilizer of 0.5-8 weight part, the photostabilizer of 0-1 weight part, the lubricant of 0-3 weight part, the antistatic agent of 0-9 weight part, the chlorinatedpolyethylene of 0-9 weight part;
Described thermo-stabilizer is lead salt stabilizer, organotin stabilizer, rare-earth stabilizer, described photostabilizer is ultraviolet absorbent UV-531, UV-9, UV-326, described lubricant is polyethylene wax, stearic acid, calcium stearate, lead stearate, and described antistatic agent is superconduction carbon black, sodium lauryl sulphate, Soxylat A 25-7.
Described lime carbonate joins in the polyvinyl chloride (PVC) Compound, can improve the dimensional stability of polrvinyl chloride product, reduces cost.Can according to circumstances regulate the consumption of lime carbonate.Demand according to the polrvinyl chloride product service condition can not added lime carbonate, also can add the lime carbonate of 15 weight parts in the polyvinyl chloride (PVC) Compound of 100 weight parts.
Described titanium dioxide joins in the polyvinyl chloride (PVC) Compound, can improve the weathering resistance of polyvinyl chloride, improves the whiteness of polrvinyl chloride product.According to the field of employment of polrvinyl chloride product, regulate the consumption of titanium dioxide.
Described thermo-stabilizer joins in the polyvinyl chloride (PVC) Compound, can improve the thermostability of polyvinyl chloride, prevents the thermal destruction of polyvinyl chloride.When the field of employment temperature of polrvinyl chloride product is higher, can suitably increase its consumption.
Described photostabilizer joins in the polyvinyl chloride (PVC) Compound, can improve the light stability of polyvinyl chloride, prevents the photodegradation of polyvinyl chloride.Be subjected to the optical radiation situation in the use according to polrvinyl chloride product, regulate its consumption.When the occasion that is not subjected to optical radiation or light radiation intensity are more weak, can not add photostabilizer.
Described lubricant joins in the polyvinyl chloride (PVC) Compound, can reduce the friction of the melt and the processing units of polyvinyl chloride (PVC) Compound, improves the flowability of melt, guarantees carrying out smoothly of processing.
Described antistatic agent joins in the polyvinyl chloride (PVC) Compound, can prevent that polrvinyl chloride product from producing static.
After described polyvinyl chloride (PVC) Compound can adopt homogenizer or low-speed mixer with improved impact modifier and polyvinyl chloride and other composition blend, by extruding or the method for injection moulding is made required polyvinyl chloride (PVC) Compound goods.
Therefore according to the different purposes of polyvinyl chloride (PVC) Compound, polyvinyl chloride (PVC) Compound has different concrete prescriptions.And can be according to the purposes difference, need to adjust the intensity of polyvinyl chloride (PVC) Compound, can regulate the content of acrylic ester elastomer in acrylate nucleoid-shell graft copolymer by the content of regulating acrylate nucleoid-shell graft copolymer shell,, can partly the consumption of the different adjustment processing aid of elastomer content according to the nuclear of acrylate nucleoid-shell graft copolymer simultaneously for the processing characteristics that guarantees polyvinyl chloride (PVC) Compound and the powder fluidity energy of anti-impact modifier.In order to guarantee the powder fluidity of acrylate core-shell graft copolymer, the content height of shell is elastomer content when low, and the processing aid consumption can be less; On the contrary, the amount of shell after a little while, the processing aid consumption is some more.Make full use of the improved action of polyvinyl chloride processing aid like this to acrylate nucleoid-shell graft copolymer powder fluidity, we just can be under the prerequisite of the processing characteristics that satisfies polyvinyl chloride (PVC) Compound, improve the content of acrylate elastomer in acrylate nucleoid-shell graft copolymer to greatest extent, to improve the shock resistance of polyvinyl chloride (PVC) Compound as far as possible.
The weight percent content of the acrylic ester elastomer of the acrylate nucleoid described in the present invention-shell graft copolymer center part is greater than 80%.The content of acrylic ester elastomer is high more, and the resistance to impact shock of prepared polyvinyl chloride (PVC) Compound is high more.But increasing of acrylic ester elastomer content, make the easier phenomenon that sticks together of acrylate nucleoid-shell graft copolymer, make the mobile variation of powder, and the present invention is increased to the content of the acrylic ester elastomer of acrylate nucleoid-shell graft copolymer center part more than 80%, solved this problem by adding processing aid, overcome that the acrylic ester elastomer content of acrylate nucleoid-shell graft copolymer center part can not be higher than a difficult problem of 80% in the prior art.Therefore the resistance to impact shock of using the polyvinyl chloride (PVC) Compound that impact modifier of the present invention makes is than currently available products height.
The present invention mixes acrylate nucleoid-shell graft copolymer in the proper ratio with processing aid, because of the second-order transition temperature height of processing aid, can prevent powder adhesion, the caking of acrylate nucleoid-shell graft copolymer.Although inciting somebody to action the weight percent content of acrylic ester elastomer wherein brings up to more than 80%, but still can guarantee acrylate nucleoid-shell graft copolymer the powder adhesion, do not lump, has good flowability, can improve the resistance to impact shock of polyvinyl chloride (PVC) Compound to greatest extent, and guarantee that it has good processing properties.Therefore the present invention has solved the problem that can't resolve in the past satisfactorily, and the weight percent content of acrylic ester elastomer is higher than at 80% o'clock in the acrylate nucleoid-shell graft copolymer of impact modifier of polyvinyl chloride, and the flowability of powder descends and powder agglomeration.Do not contain any pair of key in the impact modifier of polyvinyl chloride of the present invention simultaneously, make it have good weathering resistance.
Polyvinyl chloride (PVC) Compound of the present invention is widely used in aspects such as PVC profiled material, pvc pipe material, PVC sheet material and sheet material.
Embodiment
Further specify the present invention with specific examples below.For effect of the present invention is described, but in embodiment 1-6 and comparative example 1-4, adopt identical raw material to increase the comparative of test-results.But the present invention is not limited to the raw material that these embodiment use.
Example 1-6 all adopts technical scheme of the present invention, and in comparative example 1-3, does not add processing aid in impact modifier synthetic and directly obtains impact modifier.
Example 1
This example is the detailed process of preparation polyvinyl chloride (PVC) Compound.
(1) seed latex is synthetic
Logical N behind the Sodium dodecylbenzene sulfonate of the rongalite of the ferrous sulfate of the di-isopropylbenzene hydroperoxide of the allyl methacrylate(AMA) of the water of adding 100 weight parts, 50 parts by weight of acrylic butyl esters, 0.5 weight part, 0.1 weight part, 0.002 weight part, 0.1 weight part, 0.5 weight part in the four-hole boiling flask that agitator, mercurythermometer and nitrogen pipeline are housed
2And being warming up to 65 ℃ of reactions after 10 hours, the polymeric transformation efficiency reaches 98%.The particle diameter of emulsion particle is 140nm.
(2) acrylic elastomer is synthetic
The water of adding 80 weight parts, the synthetic solid content in (1) of 30 weight parts are the rongalite of the Sodium dodecylbenzene sulfonate of the seed latex of 33wt%, 1 weight part, 0.1 weight part, the EDTA2Na salt of 0.008 weight part, 0.002 part FeSO in the four-hole boiling flask that agitator, mercurythermometer and nitrogen pipeline are housed
47H
2Behind the O, logical N
2Be warming up to 65 ℃, add in four batches at mixture the di-isopropylbenzene hydroperoxide of the allyl methacrylate(AMA) of 90 parts by weight of acrylic butyl esters, 0.9 weight part and 0.1 weight part, each 25wt% that adds monomer mixture, react the back at last consignment of and added next batch, after in the end a batch reaction finishes, be incubated 4 hours, polymerisation conversion reaches more than 98%.
(3) acrylate nucleoid-shell graft copolymer is synthetic
To being equipped with thermometer, N
2Adding 180 weight parts synthetic solid content in (2) in the four-hole boiling flask of pipeline and agitator is acrylate elastomer emulsion, the Sodium dodecylbenzene sulfonate of 0.1 weight part, the softening water of 10 weight parts, the rongalite of 0.02 weight part, the EDTA2Na of 0.002 weight part, the FeSO of 0.001 weight part of 50wt%
47H
2The di-isopropylbenzene hydroperoxide of the methyl methacrylate of O, 9 weight parts, 1 parts by weight of acrylic ethyl ester and 0.01 part, logical N
2And be warming up to 65 ℃, and reacting after 3 hours, transformation efficiency is 98%.Wherein the content of acrylate elastomer is 90wt%, records second-order transition temperature with the DMA method and is-48 ℃; The content of grafted multipolymer shell is 10wt%.The latex particle size that is recorded acrylate core-shell graft copolymer by electron microscope is 290nm, and the second-order transition temperature that records shell with the DMA method is 82 ℃.
(4) processing aid is synthetic
To being equipped with thermometer, N
2The methyl methacrylate of the softening water of adding 60 weight parts, 36 weight parts, 4 parts by weight of acrylic butyl esters, the sodium lauryl sulphate of 0.4 weight part, the Potassium Persulphate of 0.12 weight part in the four-hole boiling flask of pipeline and agitator are opened and are stirred logical N
2Be warming up to 60 ℃, reacted 3 hours, transformation efficiency is 98%.
(5) improved acrylic ester impact-resisting modifier is synthetic
The emulsion that synthetic contains the processing aid of 20 weight parts in the emulsion that synthetic in (3) is contained 80 parts by weight of acrylic ester graft copolymers and (4) adds and mixes the calcium chloride cohesion, the centrifuge dehydration that add 5 weight parts after 1 hour in the four-hole boiling flask that is equipped with agitator, is drying to obtain acrylate impact modifier.Wherein acrylate graft copolymers content is 80wt%, and the content that adds auxiliary agent is 20wt%, and the content of acrylate elastomer is 90wt% in the acrylate graft copolymers.
(6) polyvinyl chloride (PVC) Compound
Synthetic acrylic ester impact-resisting modifier in the step (5) is made polyvinyl chloride (PVC) Compound according to following prescription, with the resistance to impact shock of test polyvinyl chloride (PVC) Compound.
Polyvinyl chloride (PVC) Compound composed as follows:
100 parts of polyvinyl chloride
7.5 parts of improved impact modifiers
2 parts of tribasic lead sulfates
1 part of dibasic Lead Phosphite
1 part of lead stearate
0.5 part of calcium stearate
0.15 part of polyethylene wax
Various raw materials are added the homogenizer high speed by above-mentioned formula rate mix, reach 120 ℃ after the discharging cooling, obtain polyvinyl chloride (PVC) Compound.
From the building-up process of the improved acrylic ester impact-resisting modifier of step (5), the improved impact modifier of 7.5 weight parts of polyvinyl chloride 100 weight parts adding wherein contains 6 parts the acrylic ester graft copolymer and the processing aid of 1.5 weight parts as can be seen.
Example 2-6
The synthetic method of example 2-6 is identical with embodiment 1 with technology, with the difference of embodiment 12 points is arranged:
1. change the consumption of the acrylate elastomer emulsion in step (3) acrylate graft copolymers synthetic, with the content that changes acrylate elastomer in the acrylate graft copolymers and the content of graft copolymer shell.
2. change the consumption of the acrylate graft copolymers in step (5) acrylate impact modifier synthetic and the consumption of processing aid, to change the two content in acrylate impact modifier.
The content of the content of acrylate elastomer, graft copolymer shell and acrylate graft copolymers, processing aid sees Table 1 among the example 2-6.
The particle diameter of the latex of acrylate core-shell graft copolymer of the example 2-6 that is recorded by electron microscope is 260-310nm, all greater than 150nm.The second-order transition temperature of measuring shell with the DMA method is 82-83 ℃, and the second-order transition temperature of the acrylic ester elastomer of nuclear part is-48 ℃.
Comparative example 1
Synthetic and the acrylate graft copolymers of synthetic, the acrylate elastomer of seed latex synthetic identical with embodiment 1.Just do not adopt the method for the present invention shown in the embodiment 1 in the comparative example 1, but be that directly cohesion of acrylate graft copolymers, centrifugation, the drying of 90wt% obtains impact modifier acrylic elastomer content.
Comparative example 2～3
Comparative example 2～3 synthetic methods are identical with comparative example 1, just changed the content of acrylic elastomer in the acrylate graft copolymers, and concrete data are as shown in table 1.
Comparative example 4
The synthetic method of comparative example 4 is identical with example 1, just the content of acrylic elastomer in the acrylate graft copolymers is changed into 75%.
Measure the resistance to impact shock of the polyvinyl chloride (PVC) Compound that example 1-6 and comparative example 1-4 obtain according to ISO179:2000, the results are shown in table 1.
Table 1 experimental test result
*
| Example | Elastomer content in the acrylic ester graft copolymer (wt%) | The composition of improved impact modifier and content (wt%) | Powder property | Resistance to impact shock (KJ/m 2) ??23℃ | |
| Acrylic ester graft copolymer | Processing aid | ||||
| Example 1 | ??90 | ??80 | ????20 | Good fluidity | ??25.0 |
| Example 2 | ??95 | ??75 | ????25 | Good fluidity | ??29.1 |
| Example 3 | ??85 | ??90 | ????10 | Good fluidity | ??22.4 |
| Example 4 | ??82 | ??97 | ????3 | Good fluidity | ??21.1 |
| Example 5 | ??90 | ??85 | ????15 | Good fluidity | ??24.7 |
| Example 6 | ??85 | ??95 | ????5 | Good fluidity | ??22.6 |
| Comparative example 1 | ??90 | ??100 | ????0 | Caking | ??12.4 * |
| Comparative example 2 | ??85 | ??100 | ????0 | Mobile bad | ??12.6 * |
| Comparative example 3 | ??75 | ??100 | ????0 | Good fluidity | ??15.1 |
| Comparative example 4 | ??75 | ??80 | ????20 | Good fluidity | ??16.2 |
Annotate:
*The expression powder lumps, mobile poor, can't with the polyvinyl chloride uniform mixing,
*The content of acrylic ester graft copolymer is and contains 6 parts of acrylic ester graft copolymers in 100 parts of polyvinyl chloride in all polyvinyl chloride (PVC) Compound; The second-order transition temperature that records the shell part of all acrylic ester graft copolymers with the DMA method is 82-83 ℃, and the second-order transition temperature of nuclear part is-48 ℃; The particle diameter of the latex of acrylate core-shell graft copolymer is all between 260-310nm, greater than 150nm in the table.
As can be seen from Table 1, in embodiment 1-6, although the weight percent content of acrylate elastomer is more than 80% in the acrylate graft copolymers and since with the processing aid blend after improved its powder characteristic, so the powder flowbility of impact modifier is all very good.And by comparative example 1-3 as can be seen, if do not add processing aid, then the weight percent content of acrylate elastomer can not be higher than 80% in the acrylate graft copolymers.Be higher than 80%, shown in comparative example 1-2, the powder flowbility of gained impact modifier is poor, even caking.
Example 1-6 from table 1 can find out that resistance to impact shock is directly proportional with the content of acrylate elastomer, and elastomer content is big more, and then shock strength is high more.In comparative example 1～2,,,, fail and the polyvinyl chloride uniform mixing, so resistance to impact shock is not high because powder fluidity is poor, caking is serious respectively at 90wt% and 85wt% although the content of acrylate elastomer is also very high.In comparative example 3,4, although powder fluidity is fine, can mix, because the content of acrylate elastomer is less than 80wt%, so the resistance to impact shock value is also lower with polyvinyl chloride.Therefore polyvinyl chloride acrylic ester impact-resisting modifier of the present invention has good processing characteristics and shock resistance, with good weathering resistance.
Example 7
This example is for the example of preparation polyvinyl chloride acrylic ester impact-resisting modifier, in order to further specify the present invention.
(1) seed latex is synthetic
Logical N behind the EDTA of the Sodium dodecylbenzene sulfonate of the rongalite of the ferrous sulfate of the di-isopropylbenzene hydroperoxide of the Vinylstyrene of the water of adding 100 weight parts, the different monooctyl ester of 50 parts by weight of acrylic, 0.5 weight part, 0.1 weight part, 0.002 weight part, 0.1 weight part, 0.5 weight part, 0.008 weight part in the four-hole boiling flask that agitator, mercurythermometer and nitrogen pipeline are housed
2And being warming up to 65 ℃ of reactions after 10 hours, the polymeric transformation efficiency reaches 98%.The particle diameter of latex granule is 135nm.
(2) acrylic elastomer is synthetic
The synthetic solid content in (1) that adds water, 30 weight parts of 80 weight parts in the four-hole boiling flask that agitator, mercurythermometer and nitrogen pipeline are housed is the EDTA of the rongalite of the Sodium dodecylbenzene sulfonate of the seed latex of 33wt%, 1 weight part, 0.1 weight part, 0.008 weight part, 2Na salt, 0.002 part FeSO
47H
2Behind the O, logical N
2Be warming up to 65 ℃, add in four batches at mixture the di-isopropylbenzene hydroperoxide of the propyl methacrylate of 45 parts by weight of acrylic butyl esters, the different monooctyl ester of 45 parts by weight of acrylic, 0.9 weight part and 0.1 weight part, each 25wt% that adds monomer mixture, react the back at last consignment of and added next batch, after in the end a batch reaction finishes, be incubated 4 hours, polymerisation conversion reaches more than 98%.
(3) acrylic ester graft copolymer is synthetic
To being equipped with thermometer, N
2Adding 180 weight parts synthetic solid content in (2) in the four-hole boiling flask of pipeline and agitator is acrylate elastomer emulsion, the Sodium dodecylbenzene sulfonate of 0.1 weight part, the softening water of 10 weight parts, the rongalite of 0.02 weight part, the EDTA2Na of 0.002 weight part, the FeSO of 0.001 weight part of 50wt%
47H
2The di-isopropylbenzene hydroperoxide of the methyl methacrylate of O, 9 weight parts, 1 parts by weight of acrylic ethyl ester and 0.01 part, logical N
2And be warming up to 65 ℃, and reacting after 3 hours, transformation efficiency is 98%.Wherein the content of acrylic ester elastomer is 90wt%, records second-order transition temperature with the DMA method and is-57 ℃; The content of grafted multipolymer shell is 10wt%, and recording second-order transition temperature with the DMA method is 83 ℃; The particle diameter of the latex that records with electron microscope is 280nm.
(4) processing aid is synthetic
To being equipped with thermometer, N
2Add the methyl methacrylate, 4 parts by weight of acrylic butyl esters, the sodium lauryl sulphate of 0.4 weight part, the Potassium Persulphate of 0.12 weight part of softening water, 36 weight parts of 260 weight parts in the four-hole boiling flask of pipeline and agitator, open and stir logical N
2Be warming up to 60 ℃, reacted 3 hours, transformation efficiency is 98%.
(5) improved acrylic ester impact-resisting modifier is synthetic
The emulsion that synthetic contains the processing aid of 20 weight parts in the emulsion that synthetic in (3) is contained 80 parts by weight of acrylic ester quasi-graft copolymers and (4) adds to mix in the four-hole boiling flask that is equipped with agitator after 1 hour and adds 0.5 weight part calcium chloride cohesion, centrifuge dehydration, is drying to obtain acrylate impact modifier.Wherein acrylic ester graft copolymer content is 80wt%, and the content that adds auxiliary agent is 20wt%.
(6) polyvinyl chloride (PVC) Compound
Polyvinyl chloride (PVC) Compound composed as follows:
100 parts of polyvinyl chloride
7.5 parts of improved impact modifiers
2 parts of tribasic lead sulfates
1 part of dibasic Lead Phosphite
1 part of lead stearate
0.5 part of calcium stearate
5 parts in lime carbonate
0.15 part of polyethylene wax
4 parts of titanium dioxides
Various raw materials are added the homogenizer high speed by above-mentioned formula rate mix, reach 120 ℃ after the discharging cooling, obtain polyvinyl chloride (PVC) Compound.
After tested, the powder property good fluidity, resistance to impact shock is 26.1kJ/m
2
Comparative example 5
This comparative example has prepared the acrylic ester impact-resisting modifier of the particle diameter of acrylic ester graft copolymer less than 150nm, has tested its shock strength according to the prescription and the method for example 1 then, to further specify the present invention.
(1) seed latex is synthetic
The water of adding 100 weight parts, 50 parts by weight of acrylic butyl esters, the allyl methacrylate(AMA) of 0.5 weight part, the Potassium Persulphate of 0.1 weight part in the four-hole boiling flask that agitator, mercurythermometer and nitrogen pipeline are housed, logical N behind the Sodium dodecylbenzene sulfonate of 3 weight parts
2And after being warming up to 65 ℃ of reaction 10h, the polymeric transformation efficiency reaches 98%.The particle diameter of emulsion particle is 75nm.
(2) acrylic elastomer is synthetic
The synthetic solid content in (1) that adds water, 100 weight parts of 60 weight parts in the four-hole boiling flask that agitator, mercurythermometer and nitrogen pipeline are housed is to lead to N behind the Potassium Persulphate of the Sodium dodecylbenzene sulfonate of the seed latex of 33wt%, 3 weight parts, 0.1 weight part
2Be warming up to 65 ℃, add in four batches at mixture the allyl methacrylate(AMA) of 90 parts by weight of acrylic butyl esters, 0.9 weight part, each 25wt% that adds monomer mixture, react the back at last consignment of and added next batch, after in the end a batch reaction finishes, insulation 4h, polymerisation conversion reaches more than 98%.
(3) acrylate nucleoid-shell graft copolymer is synthetic
To being equipped with thermometer, N
2Adding 180 weight parts synthetic solid content in (2) in the four-hole boiling flask of pipeline and agitator is acrylate elastomer emulsion, the Sodium dodecylbenzene sulfonate of 0.1 weight part, the softening water of 10 weight parts, the Diao Bai piece of 0.02 weight part, the EDTA2Na of 0.002 weight part, the FeSO of 0.001 weight part of 50wt%
47H
2The di-isopropylbenzene hydroperoxide of the methyl methacrylate of O, 9 weight parts, 1 parts by weight of acrylic ethyl ester and 0.01 part, logical N
2And be warming up to 65 ℃, and reacting after 3 hours, transformation efficiency is 98%.Wherein the weight percent content of acrylic ester elastomer is 90%, and the second-order transition temperature that records with the DMA method is-48 ℃; The weight percent content of grafted multipolymer shell is 10%, and the second-order transition temperature that records with the DMA method is 82 ℃.The particle diameter of the latex of acrylate core-shell graft copolymer is 125nm.
(4) processing aid is synthetic
To being equipped with thermometer, N
2The methyl methacrylate of the softening water of adding 60 weight parts, 36 weight parts, 4 parts by weight of acrylic butyl esters, the sodium lauryl sulphate of 0.4 weight part, the Potassium Persulphate of 0.12 weight part in the four-hole boiling flask of pipeline and agitator are opened and are stirred logical N
2Be warming up to 60 ℃, reacted 3 hours, transformation efficiency is 98%.
(5) acrylic ester impact-resisting modifier is synthetic
The emulsion that synthetic contains the processing aid of 20 weight parts in the emulsion that synthetic in (3) is contained 80 parts by weight of acrylic ester nucleoid-shell graft copolymer and (4) adds and mixes the calcium chloride cohesion, the centrifuge dehydration that add 5 weight parts after 1 hour in the four-hole boiling flask that is equipped with agitator, is drying to obtain acrylate impact modifier.Wherein acrylate graft copolymers content is 80wt%, and the content that adds auxiliary agent is 20wt%.
(6) test of shock resistance
Synthetic acrylic ester impact-resisting modifier in (5) is made polyvinyl chloride (PVC) Compound according to following prescription, to test its shock strength.
Polyvinyl chloride (PVC) Compound composed as follows:
100 parts of polyvinyl chloride
7.5 parts of improved impact modifiers
2 parts of tribasic lead sulfates
1 part of dibasic Lead Phosphite
1 part of lead stearate
0.5 part of calcium stearate
0.15 part of polyethylene wax
Various raw materials are added the homogenizer high speed by above-mentioned formula rate mix, reach 120 ℃ after the discharging cooling, obtain polyvinyl chloride (PVC) Compound.
After tested, the acrylic ester impact-resisting modifier powder fluidity of this comparative example is good, and still the resistance to impact shock with the polychloroethylene blended mixture that obtains is 16.1KJ/m
2, in this comparative example in acrylate core-shell graft copolymer the weight percent content of acrylic elastomer identical with example 1, be 90% all, nuclear is all identical with the second-order transition temperature of shell and composition.Because the particle diameter of the acrylate core-shell graft copolymer of example 1 is 290nm, so resistance to impact shock is 25.0KJ/m greater than 150nm
2Far above this comparative example.
Comparative example 6
This comparative example has prepared the second-order transition temperature of shell of acrylic ester graft copolymer less than 50 ℃ acrylic ester impact-resisting modifier, has tested its shock strength according to the prescription and the method for example 1 then, to further specify the present invention.
The synthetic method of comparative example 6 is identical with example 1 with technology, have a bit with the difference of example 1, in (3) acrylate nucleoid-shell graft copolymer synthetic, the shell monomers mixture of example 1 is methyl methacrylate, the 1 parts by weight of acrylic ethyl ester of 9 weight parts, and the shell second-order transition temperature of synthetic acrylic ester graft copolymer is 82 ℃.And the shell monomers mixture of comparative example 6 is methyl methacrylate, the 6 parts by weight of acrylic ethyl esters of 4 weight parts, and the shell second-order transition temperature of synthetic acrylic ester graft copolymer is 42 ℃, less than 50 ℃ of claim values of the present invention.
The resulting acrylic ester impact-resisting modifier powder fluidity of this comparative example descends, caking phenomenon is arranged, can not mix with polyvinyl chloride, under the situation all identical with testing method with the prescription of the polyvinyl chloride (PVC) Compound of example 1, the resistance to impact shock of the polyvinyl chloride (PVC) Compound of preparation is 17.6KJ/m
2
Comparative example 7
This comparative example has prepared the second-order transition temperature of acrylic elastomer of nuclear of acrylic ester graft copolymer greater than-20 ℃ acrylic ester impact-resisting modifier, tested its shock strength according to the prescription and the method for the polyvinyl chloride (PVC) Compound of example 1 then, to further specify the present invention.
The synthetic method of this comparative example is identical with example 1 with technology, have a bit with the difference of example 1, in (2) acrylic ester elastomer synthetic, the monomer mixture of example 1 is the allyl methacrylate(AMA) of 90 parts by weight of acrylic butyl esters, 0.9 weight part, and the second-order transition temperature of synthetic acrylic ester elastomer is-48 ℃.And being the second-order transition temperature of acrylic ester elastomer of nuclear of allyl methacrylate(AMA) synthetic acrylic ester graft copolymer of methyl methacrylate, 70 parts by weight of acrylic butyl esters and 0.9 weight part of 20 weight parts, the monomer mixture of comparative example 7 is-12 ℃, greater than claim value-20 of the present invention ℃.
The resulting acrylate impact modifier powder fluidity of this comparative example is good, and under the situation all identical with testing method with the prescription of the polyvinyl chloride (PVC) Compound of example 1, the resistance to impact shock of the polyvinyl chloride (PVC) Compound of preparation is 16.3KJ/m
2
Claims (8)
1. the polyvinyl chloride acrylic ester impact-resisting modifier of a weathering resistance, shock resistance, excellent processability is made by following weight percentages: acrylate nucleoid-shell graft copolymer 65-97%, processing aid 3-35%, described acrylate nucleoid-shell graft copolymer partly is made up of nuclear part and shell, the nuclear part is an acrylic ester elastomer, and the weight percent content of acrylic ester elastomer in acrylate nucleoid-shell graft copolymer is greater than 80%.
2. impact modifier according to claim 1, its special being, the second-order transition temperature of described acrylic ester elastomer is less than-20 ℃, and the second-order transition temperature of described shell part is greater than 50 ℃.
3. impact modifier according to claim 1, its special being, the number average bead diameter of emulsion particle is 150-500nm in the latex of described acrylate nucleoid one shell graft copolymer.
4. impact modifier according to claim 3 is characterized in that: the latex of described acrylate nucleoid-shell graft copolymer is prepared from by following method:
(1) seed latex is synthetic: with the tensio-active agent of the radical initiator of the linking agent that contains two or more carbon-carbon double bonds of the water of 80-120 weight part, 40-60 parts by weight of acrylic alkyl ester, 0.01-3 weight part, 0.001-1 weight part, 0.1-2 weight part, join in the reactor, in nitrogen atmosphere, be warming up to 50-80 ℃, with 100-500 rev/min speed stirring reaction 6-10 hour, obtain the seed latex that number average bead diameter is 120-160nm;
(2) the acrylic ester elastomer emulsion is synthetic: with the water of 60-100 weight part, the seed latex that the step of 20-80 weight part (1) obtains, 0.3-1.5 the tensio-active agent of weight part joins in the reactor, in nitrogen atmosphere, be warming up to 50-80 ℃, under 100-500 rev/min speed agitation condition again with 80-100 parts by weight of acrylic alkyl ester, 0.01-5 the linking agent that contains two or more carbon-carbon double bonds of weight part and the radical initiator of 0.001-1 weight part are divided into 2-4 and criticize adding, each timed interval that adds is 1-3 hour, is incubated the emulsion that obtained containing acrylic ester elastomer in 3-5 hour then;
(3) acrylate nucleoid-shell graft copolymer is synthetic: the emulsion that contains 150-200 parts by weight of acrylic acid ester elastomer that step (2) is obtained, the water of 1-25 weight part, 0.01-0.5 the tensio-active agent of weight part, the alkyl methacrylate of 1-25 weight part, 0-2.5 the radical initiator of parts by weight of acrylic alkyl ester and 0.001-0.2 weight part joins in the reactor, under nitrogen atmosphere, be warming up to 50-80 ℃, with down reaction 3-5 hour of 100-500 rev/min speed agitation condition, obtaining the acrylate elastomer weight percent content is the emulsion of acrylate nucleoid-shell graft copolymer of 150-500nm greater than 80% number average bead diameter.
5. impact modifier according to claim 4 is characterized in that: the described linking agent that contains two or more carbon-carbon double bonds is allyl methacrylate(AMA), Vinylstyrene, Phthalic acid, diallyl ester, allyl acrylate, Ethylene glycol dimethacrylate, ethylene glycol diacrylate, Phthalic acid, diallyl ester, Viscoat 295, trimethylolpropane trimethacrylate.
6. impact modifier according to claim 1 is characterized in that: described processing aid is selected from following processing aid A, B, C, D, E, F, and they are made by following preparation method respectively:
(1) processing aid A: the alkyl methacrylate of the water of 50-70 weight part, 30-40 weight part, 0-20 parts by weight of acrylic alkyl ester, the tensio-active agent of 0.1-1 weight part, the radical initiator of 0.001-0.2 weight part are joined in the reactor, to be warming up to 50-80 ℃ under 50-500 rev/min the speed stirring, reacted 2-4 hour;
(2) processing aid B: the alpha-methyl styrene of the vinyl cyanide of the vinylbenzene of the water of 50-70 weight part, 20-25 weight part, 1-10 weight part, 0-10 weight part, 0-10 parts by weight of acrylic alkyl ester, the tensio-active agent of 0.1-1 weight part, the radical initiator of 0.001-0.2 weight part are joined in the reactor, to be warming up to 50-80 ℃ under 50-500 rev/min the speed stirring, reacted 2-4 hour;
(3) processing aid C:
The emulsion of described processing aid A and the emulsion mixing of described processing aid B are obtained, and wherein the weight percent content of processing aid A, B emulsion is: described processing aid A 0-100%, described processing aid B 0-100%;
(4) processing aid D: the alkyl methacrylate of the water of 100 weight parts, 0-100 weight part, 0-30 parts by weight of acrylic alkyl ester, the vinylbenzene of 0-85 weight part, the vinyl cyanide of 0-40 weight part, the tensio-active agent of 0.1-2 weight part, the radical initiator of 0.001-1 weight part are joined in the reactor, to be warming up to 50-80 ℃ under 50-500 rev/min the speed stirring, reacted 2-4 hour;
(5) processing aid E: the monomer mixture that adds the emulsion of processing aid B in the emulsion of processing aid A joins in the reactor, to be warming up to 50-80 ℃ under 50-500 rev/min the speed stirring, reaction obtained the emulsion of processing aid E in 2-4 hour, and wherein the weight percent content of the emulsion of processing aid A is that the weight percent content of monomer mixture of the emulsion of 0-100%, processing aid B is 0-100%;
(6) processing aid F: the monomer mixture that adds the emulsion of processing aid A in the emulsion of processing aid B joins in the reactor, to be warming up to 50-80 ℃ under 50-500 rev/min the speed stirring, reaction obtained the emulsion of processing aid F in 2-4 hour, and wherein the weight percent content of the emulsion of processing aid B is that the weight percent content of monomer mixture of the emulsion of 0-100%, processing aid A is 0-100%.
7. according to claim 4,6 described impact modifiers, it is characterized in that: the carbonatoms of the alkyl of described alkyl acrylate is 2-8, the carbonatoms of the alkyl of described alkyl methacrylate is 1-8, described radical initiator is di-isopropylbenzene hydroperoxide, Potassium Persulphate, ammonium persulphate, Sodium Persulfate, tertbutyl peroxide, hydrogen phosphide cumene, and described tensio-active agent is Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, sodium stearate, potassium stearate.
8. impact modifier according to claim 7, it is characterized in that: described alkyl acrylate is selected from vinylformic acid propyl diester, butyl acrylate cores, vinylformic acid amyl group ester, Isooctyl acrylate monomer, vinylformic acid heptyl ester, described alkyl methacrylate is selected from methyl methacrylate, methacrylic acid propyl diester, methacrylic acid butyl ester, methacrylic acid amyl group ester, Isooctyl methacrylate, methacrylic heptyl heptylate.
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| CN100393793C (en) * | 2005-09-30 | 2008-06-11 | 赵东日 | Polyvinyl chloride processing plasticizing modifier, its preparation method and application |
| CN100393794C (en) * | 2005-10-28 | 2008-06-11 | 赵东日 | Polychloroethylene processing modifier and its preparation process and application thereof |
| CN100439407C (en) * | 2005-06-29 | 2008-12-03 | 赵东日 | Polyvinyl chloride processing plasticizing modifier, its preparation method and application |
| CN102464841A (en) * | 2010-11-19 | 2012-05-23 | 山东博拓塑业股份有限公司 | Hard polyvinyl chloride foamed sheet |
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| CN100393793C (en) * | 2005-09-30 | 2008-06-11 | 赵东日 | Polyvinyl chloride processing plasticizing modifier, its preparation method and application |
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Owner name: SHANDONG RIKE CHEMICAL CO., LTD. Free format text: FORMER OWNER: ZHAO DONGRI Effective date: 20091127 |
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| C41 | Transfer of patent application or patent right or utility model | ||
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Effective date of registration: 20091127 Address after: 500 meters south of science and technology two street, Changle Economic Development Zone, Weifang, Shandong Patentee after: Shandong Rike Chemical Co., Ltd. Address before: Gem County, Changle City, Shandong Province Patentee before: Zhao Dongri |
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Decision date of declaring invalidation: 20120829 Decision number of declaring invalidation: 19217 Granted publication date: 20060308 |