CN1052250C - Radio pager having function switches for establishing an additional function of coupling the pager with an external device - Google Patents
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- CN1052250C CN1052250C CN 92103096 CN92103096A CN1052250C CN 1052250 C CN1052250 C CN 1052250C CN 92103096 CN92103096 CN 92103096 CN 92103096 A CN92103096 A CN 92103096A CN 1052250 C CN1052250 C CN 1052250C
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Abstract
The present invention relates to a vinyl chloride resin composite, and both the impact strength and the transparence of the composite are better than those of vinyl chloride resin. The preparation method comprises the steps: (a) grafting copolymer, (i) adding water-solubility dielectric to butadiene polymer (a), (ii) adding monomer mixtures (b) mainly containing vinyl monomers of an aromatic group and carrying out polymerization, (iii) adding monomer mixtures (c) mainly containing alkyl methacrylic acid ester and carrying out the polymerization, and (iv) if necessary, adding the monomer mixtures mainly containing the vinyl monomers of the aromatic group.
Description
The present invention relates to vinyl chloride resin composition, particularly shock strength is improved and the vinylchlorid of the original excellent transparency of vinyl chloride resin itself.
Graft polymerization such as methyl methacrylate and vinylbenzene has been used as the toughener that improves the vinyl chloride resin shock strength to the so-called MBS resin on the divinyl rubber.Importantly the resin transparent degree not essential factor add toughener and suffer damage.Proposed multiple improvement vinyl chloride resin toughener and improve the vinyl chloride resin shock strength and don't damage the measure of the method for its transparency.But require the cry of improvement vinyl chloride resin quality product still very high, require further to improve.
Form the shock strength that macrobead can improve the MBS resin as known with small-particle.Therefore proposed the agglomeration technique of various MBS resin particles, seen as open № .42-22541 of Japan's unexamined patent and 46-31462 etc.But generally mix with vinyl chloride resin at big particle diameter MBS resin, the vinyl chloride resin composition transparency that obtains reduces.All good as above-mentioned extremely inaccessible shock strength and transparency, and the performance of the utmost importance that these two kinds of performances are vinyl chloride resin composition.
The present invention seeks to solve this big shortcoming of the method that transparency reduces, wherein adopting increases MBS resin particle diameter as obviously improving the measure of shock strength and don't can undermining the method for the ability of vinyl chloride resin toughener (MBS resin).
Another purpose of the present invention is to propose shock strength and all good vinyl chloride resin composition of transparency.
Above-mentioned and other purpose of the present invention sees for details in following.
The present invention proposes vinyl chloride resin composition, comprising:
(A) 1-30 weight % graft copolymer and
(B) 99-70 weight % vinyl chloride resin;
This graft copolymer method for making is
(i) water-soluble ionogen is added in the latex aqueous solution, this aqueous solution contains 50-85 weight parts of butadiene polymkeric substance (a), this polymkeric substance comprises 60-100 weight % divinyl, 40-0 weight % aromatic vinyl monomer, 10-0 weight % is the vinyl monomer and the 5-0 weight % cross-linking monomer of copolymerization with it, this butadiene polymer (a) median size is less than 0.1 μ m
(ii) 1-45 weight parts monomers mixture (b) is added in the latex and carries out polymerization,
Monomer mixture (b) comprises 51-100 weight % aromatic vinyl monomer, and 49-0 weight % alkyl methacrylate and 0-20 weight % be the vinyl monomer of copolymerization with it,
(iii) add the monomer mixture (c) of 5-45 weight part in the step polyblend (ii) and carry out polymerization,
Monomer mixture (c) comprises 51-100 weight % alkyl methacrylate, 49-0 weight % aromatic vinyl monomer and 0-20 weight % with it copolymerization vinyl monomer and
(iv) 0-30 weight parts monomers mixture (d) is added in the step polyblend (iii) and carries out polymerization,
This monomer mixture comprises 51-100 weight % aromatic vinyl monomer, and 49-0 weight % alkyl methacrylate and 0-20 weight % be the vinyl monomer of copolymerization with it;
Polymkeric substance (a), mixture (b), the total amount of mixture (c) and mixture (d) is 100 weight parts.
The latex aqueous solution that is used for butadiene polymer of the present invention (a) is 60-100 weight % divinyl, 40-0 weight % aromatic vinyl monomer, 10-0 weight % be the latex aqueous solution of the butadiene polymer (a) of the vinyl monomer of copolymerization (i) and 0-5 weight % cross-linking monomer with it.Butadiene polymer (a) median size is less than 0.1 μ m.Available for example emulsion polymerization obtains this latex aqueous solution.
Aromatic vinyl monomer is just to use when the specific refraction of the butadiene polymer that requires to improve generation (a), and its example can be as vinylbenzene etc.And but copolyethylene monomer (i) example is as vinyl cyanide monomer, and as vinyl cyanide, vinylformic acid 1-5 carbon alkyl ester is as vinylformic acid ethyl ester or butyl acrylate cores etc.The linking agent examples of monomers is as Vinylstyrene etc.But aromatic vinyl monomer, but copolyethylene monomer (i) and cross-linking monomer are not limited in above-mentioned example, and also they can be distinguished separately or use with its mixture.
The divinyl consumption contains 60-100 weight % with generation, and the butadiene polymer (a) of preferred 70-85 weight % divinyl is as the criterion, and when wherein content was lower than 60 weight %, gained vinyl chloride resin composition shock strength can reduce.
And aromatic vinyl monomer, but copolyethylene monomer (i) and amount ofthe cross-linking monomer should contain 40-0 weight % aromatic vinyl monomer with generation, but the butadiene polymer (a) of 10-0 weight % copolyethylene monomer and 0-5 weight % cross-linking monomer is as the criterion.From effective raising butadiene polymer (a) performance, polymkeric substance (a) preferably contains 30-15 weight % aromatic vinyl monomer, 5-0 weight % copolymerisable monomer and 0-2 weight % cross-linking monomer.During more than 40 weight %, butadiene content just very little at aromatic vinyl monomer content.But during more than 10 weight %, the composition shock strength can reduce at copolyethylene monomer (i) content.During more than 5 weight %, the composition shock strength also can reduce at cross-linking monomer content.
Butadiene polymer (a) median size is less than 0.1 μ m, preferred 0.07-0.08 μ m.When median size is not less than 0.1 μ m, be difficult to make MBS resin particle caking, and the resulting composition shock strength some is poor.
Among the present invention water-soluble ionogen adding is contained in the latex aqueous solution of 50-85 weight parts of butadiene polymkeric substance (a) the about 50-25 weight of solids concn % in this latex.In the gained latex aqueous solution, add 1-45 weight parts monomers mixture (b) then and carry out polymerization (the first step graft polymerization), comprise 51-100 weight % aromatic vinyl monomer in the monomer mixture (b), 49-0 weight % alkyl methacrylate and 0-20 weight % with it copolymerization vinyl monomer (ii).In the reaction mixture of the first step graft polymerization, add 5-45 weight parts monomers mixture (c) afterwards and carry out polymerization (the second step graft polymerization), (c) comprises 51-100 weight % alkyl methacrylate in the monomer mixture, 49-0 weight % aromatic vinyl monomer and 0-20 weight % with it copolymerization vinyl monomer (iii).In the reaction mixture of the second step graft polymerization, add at last 0-30 weight parts monomers mixture (d) and carry out polymerization (the 3rd step graft polymerization) and graft copolymer (A), comprise 51-100 weight % aromatic vinyl monomer in the monomer mixture (d), 49-0 weight % alkyl methacrylate and 0-20 weight % with it copolymerization vinyl monomer (ii).Polymkeric substance (a) and mixture (b), (c) and (d) total amount is 100 weight parts.Use among the present invention and so make and the graft copolymer (A) of median size 0.1-0.3 μ m.
Because of the present invention uses the above-mentioned graft copolymer that makes (A), so vinyl chloride resin (B) transparency and shock strength are all very high, its multipolymer (A) method for making is that monomer mixture (b) graft polymerization that will mainly contain aromatic vinyl monomer upward gets multipolymer (1) to butadiene polymer (a), monomer mixture (c) graft polymerization that will mainly contain alkyl methacrylate then to multipolymer (1) go up and multipolymer (2), and and then monomer mixture (d) graft polymerization that will mainly contain aromatic vinyl monomer to multipolymer (2).
Water-soluble ionogen is used for making rubber grain to lump into macrobead in the graft polymerization process, and its example can be enumerated as resolving into Na
+, K
+, Mg
2+, Ca
2+, Al
3+, NH
4 +Or H
+Compound, can resolve into Cl
-, Br
-, SO
4 2-, SO
3 2-, S
2O
8 2-, NO
3 -, NO
2 -, PO
4 3-, CO
3 2-Or OH
-Compound etc., as NaCl, KCl, Na
2SO
4, CaCl
2, AlCl
3Deng.
The electrolysis amount is with 100 weight parts (a), and (b), (c) and (d) total amount is counted preferred 0.5-5, more preferably 1.0-3 weight part, and when surpassing 5 weight parts, latex instability, and the polymerization scales easily increases, and when being less than 0.5 weight part, be difficult to caking again.
The aromatic vinyl monomer that is contained in monomer mixture (b) and monomer mixture (d) (being used for the first step and the 3rd step graft polymerization) is used for making the graft copolymer (A) and the refractive index of vinyl chloride resin (B) to match, wherein improve the refractive index of graft copolymer (A), thereby improve the composition transparency, the aromatic vinyl monomer example is a vinylbenzene, alpha-methyl styrene etc.
When requiring to improve cohesiveness between graft copolymer (A) and vinyl chloride resin (B), just adopt the alkyl methacrylate that is contained in monomer mixture (b) and the monomer mixture (d) with further raising shock strength, example is as methacrylic acid 1-5 carbon alkyl ester, as methyl methacrylate etc.Copolymerisable monomer (ii) example is as vinyl cyanide monomer, as vinyl cyanide, and alkyl acrylate, as ethyl propenoate or butyl acrylate etc.Be used for the aromatic vinyl monomer of the first step graft polymerization and the 3rd step graft polymerization, alkyl methacrylate and copolymerisable monomer are not limited in above-mentioned each compound.And above-claimed cpd can be used alone or as a mixture.The aromatic vinyl monomer kind that is used for the first step and the 3rd step graft polymerization can be identical or different.Equally, but be used for the first step and the 3rd step alkyl methacrylate of graft polymerization and copolyethylene monomer kind (ii) all can be similar and different.
Monomer mixture (b) and monomer mixture (d) all can contain 51-100 weight %, preferred 70-100 weight % aromatic vinyl monomer.When aromatic vinyl monomer content was less than 51 weight %, the vinyl chloride resin composition transparency reduced.And, monomer mixture (b) and monomer mixture (d) but all can contain 49-0 weight % alkyl methacrylate and 0-20 weight % copolyethylene monomer (ii).From the performance of effective raising graft copolymer (A), each mixture (b) or (d) all contain 30-0 weight % alkyl methacrylate monomer and 0-10 weight % copolymerisable monomer (ii) preferably.During greater than 49 weight %, aromatic vinyl monomer content is just too low at alkyl methacrylate content.But when (ii) content was greater than 20 weight %, the vinyl chloride resin composition transparency will reduce at copolyethylene monomer.
The contained alkyl methacrylate of monomer mixture (c) that is used for the second step graft polymerization is used to improve the composition shock strength.Just application is contained in aromatic vinyl monomer in the monomer mixture (c) when the refractive index of the specific refraction that requires to make graftomer (A) by the refractive index that improves multipolymer (A) and vinyl chloride resin (B) is complementary with further raising composition transparency.And just use in the workability that requires to improve composition or when improving flake occurrence rate in the course of processing be contained in monomer mixture (c) but in copolyethylene monomer (iii).Can be used as the alkyl methacrylate that is contained in the monomer mixture (c) as listed same compound in monomer mixture (b) or the monomer mixture (d), but aromatic vinyl monomer and copolyethylene monomer are (iii), but these compositions are not limited in above-listed compound.
Monomer mixture (c) contains 51-100 weight %, preferred 70-100 weight % alkyl methacrylate.When alkyl methacrylate content was lower than 51wt%, the composition shock strength can reduce.
And, monomer mixture (c) but contain 49-0 weight % aromatic vinyl monomer and 0-20 weight % copolyethylene monomer (iii).Have in mind from the performance of effective raising graftomer (A), preferably mixture (c) but contain 30-0 weight % aromatic vinyl monomer and 0-10 weight % copolyethylene monomer (iii).During more than 49 weight %, the alkyl methacrylate amount just very little at aromatic vinyl monomer content.But when (iii) content was more than 20 weight %, composition transparency and shock strength will reduce at copolyethylene monomer.
Butadiene polymer (a), monomer mixture (b), the amount of monomer mixture (c) and monomer mixture (d) is respectively the 50-85 weight part, the 1-45 weight part, 5-45 weight part and 0-30 weight part, and (a), (b), (c) and (d) total amount is 100 weight parts.Monomer mixture (b) and (d) sum 5-45 weight part.Carrying out for three steps during graft polymerization, preferably (a), (b), amount (c) and (d) is respectively the 50-85 weight part, the 1-20 weight part, 5-45 weight part and 4-30 weight part, 60-80 weight part more preferably, 2-10 weight part, 10-20 weight part and 5-15 weight part, and (a), (b), (c) and (d) total amount is 100 weight parts.And, carried out for two steps during graft polymerization, preferably (a), (b) and amount (c) be respectively the 50-85 weight part, 5-45 weight part and 5-45 weight part, more preferably 60-80 weight part, 10-20 weight part and 10-20 weight part, and (a), (b) and total amount (c) be 100 weight parts.When butadiene polymer (a) was less than 50 weight parts, the composition shock strength can reduce.During more than 85 weight parts, graft copolymer (A) easily becomes oversize material and can not get common resin when aftertreatment at butadiene polymer (a).Monomer (b) and (d) the amount sum is when being less than 5 weight parts, the composition transparency can reduce, and sum is during greater than 45 weight parts, shock strength can reduce again.When monomer mixture (c) amount was less than 5 weight parts, shock strength can reduce, and its amount is during greater than 45 weight parts, and transparency can reduce again.
The first step graft polymerization just before the first step graft polymerization, adds water-soluble ionogen in butadiene polymer (a) the latex aqueous solution in not special stipulations of aspect such as reaction conditionss.The second step graft polymerization is not particularly limited at aspects such as reaction conditionss yet.But the situation that the squamous scale of construction that produces when a kind of polymerization is arranged increases, its terms of settlement are earlier monomer mixture (c) to be made emulsion and continuously the gained emulsion is added in the reaction mixture of the first step graft polymerization when second step graft polymerization.The emulsion method for making for example is that monomer mixture (c) is added with 100 weight parts (a), (b), (c) and (d) total amount is counted the 5-90 weight part, the containing with 100 weight parts (a) of preferred 10-90 weight part, (b), (c) and total amount (d) count the 0.05-3 weight part, in the aqueous solution of the emulsifying agent of preferred 0.1-1 weight part and with its mixture stirring and emulsifying, wherein the emulsifying agent example is as soap, as sodium oleate, potassium oleate or potassium palmitate, emulsifying agent commonly used etc., certain available emulsifying agent is not limited in this.
When emulsification dosage was less than 0.05 weight part, the effect that reduces the squamous scale of construction can reduce, and its amount is during greater than 3 weight parts, and gained mixture thermostability can reduce again.And, when containing the emulsifier aqueous solution amount and being less than 5 weight parts, can not make the monomer emulsification in the monomer mixture (c) reposefully, and in its amount during more than 90 weight parts, graft copolymer (A) concentration can reduce again, so output will reduce.And the emulsification measure can be taked the common way with homogenizer or line mixing tank.
Graft copolymer (A) median size 0.1-0.3 μ m, preferred 0.12-0.2 μ m.Median size improves the shock strength effect and can reduce during less than 0.1 μ m, and median size is during greater than 0.3 μ m, and transparency can obviously reduce again.
For improving final moulded product transparency, preferably the refractive index of the refractive index of this graft copolymer and vinyl chloride resin is enough approaching.In general, the difference of the refractive index of graft copolymer (A) and vinylchlorid (B) is about 0-about 0.01.
Can obtain polymerizing power with the graft copolymer of making like this (A) the latex aqueous solution, method is that acid and/or salt are added in the latex so that polymer beads easily condenses, and heat treated washes polymer beads with water, the dehydration after drying.
Gained graftomer (A) is counted 1-30 weight % in a usual manner with the total amount of 100 weight part graftomer (A) and vinyl chloride resin (B), preferred 3-30 weight %, more preferably the vinyl chloride resin of 5-15 weight % (B) mix and resin combination of the present invention.When graftomer (A) amount was less than 1 weight %, the composition shock strength can reduce, and its amount is during greater than 30 weight %, and rigidity can reduce again.
Vinyl chloride resin (B) is not particularly limited yet, available any common vinyl chloride resin or polymkeric substance, and polyvinyl chloride etc., as ryuron, content of vinylchloride is at least about vinyl chloride copolymer and the follow-up chlorinated polyvinyl chloride of 80wt%.
The present composition can contain the additive that is usually used in vinyl chloride resin, as stablizer or lubricant etc.
Resin combination of the present invention can be through making moulded product as injection molding, rolling process, blow moulding etc., and its shock strength and transparency are all good, should be used as bottle and band.
Following example describes the present invention in detail, wherein unless otherwise indicated and outer, all umbers and % all by weight, but the present invention is not limited to this.
Example 1
In the aggregation container that agitator is housed, add 200 parts of water, 1.5 parts of sodium oleates, 0.002 part of ferrous sulfate (FeSO
47H
2O), 0.005 part of disodium EDTA, 0.2 part of sodium sulfoxylate formaldehyde, 0.2 part of Tripotassium phosphate, 75 parts of divinyl, 25 parts of vinylbenzene, 1.0 parts of Vinylstyrenes and 0.1 part of diisopropylbenzene(DIPB) hydroperoxide.50 ℃ of polymerizations carry out getting in 15 hours the latex (calling " latex A " in the following text) of polymer beads median size 750 .Polymerisation conversion 99%.
In 210 parts of latex A (70 parts of solids contents), add 200 parts of water, 0.002 part of ferrous sulfate, 0.004 part of disodium EDTA, 0.1 part of sodium sulfoxylate formaldehyde and 2.3 parts of Repone K.70 ℃ add 14 parts of vinylbenzene, the mixture (b) of 1.0 parts of methyl methacrylates and 0.2 part of cumene hydroperoxide, repolymerization 30 minutes (the first step graft polymerization) in 3 hours continuously in latex then.70 ℃ add 14 parts of methyl methacrylates in 3 hours continuously afterwards, 1.0 parts of vinylbenzene and 0.1 part of cumene hydroperoxide, repolymerization 1 hour (the second step graft polymerization) and the graft polymer latex aqueous solution.
Graft polymer latex particle caking back median size 1500 .Scales that generates during graft polymerization and the weight ratio of graft copolymer 2.2%.
Sulfuric acid added in the gained graft polymer latex make polymer deposition, through thermal treatment, washing, dehydration and dry and polymer powder.
10 parts of graft copolymer powder addings are contained 1.5 parts of tin octylate thiolate stablizers, in 90 parts of polyvinyl chloride of 0.5 part of ricinoleic acid glyceryl ester and 0.2 part of montanate.Mixture was kneaded 8 minutes with 170 ℃ of rollers and is got the Izod impact test piece of thick 6mm and the zona pellucida of thick 5mm with 180 ℃ of hot pressing roll-ins 15 minutes.The Izod shock strength is measured with the JISK7110 way, and transmittance is pressed JIS K 6714 mensuration, the results are shown in table 1.
Example 2
Repeat example 1, the monomer mixture (c) that just is used for the second step graft polymerization, i.e. 14 parts of methyl methacrylates, 1.0 parts of vinylbenzene and 0.1 part of cumene hydroperoxide add the gained emulsion in the reaction mixture of the first step graft polymerization in 3 hours after with homogenizer emulsification in the aqueous solution of 0.3 part of sodium oleate and 15 parts of water continuously.
The results are shown in table 1.
Example 3
Repeat example 1, just the Repone K quantitative change is 2.7 parts, so graft copolymer median size 1800 .
The results are shown in table 1.
Example 4
Repeat example 1, just adding monomer mixture (c) before, 15.3 parts of aqueous solution that contain 0.3 part of sodium oleate are added in the reaction mixture of the first step graft polymerization.
The results are shown in table 1.
Comparative example 1
Latex A makes by example 1.
In 210 parts of latex A (70 parts of solids contents), add 200 parts of water, 0.002 part of ferrous sulfate, 0.004 part of disodium EDTA and 0.1 part of sodium sulfoxylate formaldehyde.
70 ℃ add 14 parts of methyl methacrylates in 3 hours continuously in the gained mixture, the mixture of 1.0 parts of vinylbenzene and 0.1 part of cumene hydroperoxide, and polyase 13 0 minute.
Then, add 14 parts of vinylbenzene in 3 hours continuously, the mixture of 1.0 parts of methyl methacrylates and 0.2 part of cumene hydroperoxide, and repolymerization 1 hour and the graft copolymer latex aqueous solution of median size 800 .
Make resin combination and, the results are shown in table 1 by example 1 evaluation.
Comparative example 2
Repeat comparative example 1, just the first step and the second step polymeric are turned around in proper order.
The results are shown in table 1.
Comparative example 3
Repeat comparative example 1, just with the first step with the second step polymeric turns around in proper order and with 1.5 parts of Repone K.
The results are shown in table 1.
Comparative example 4
Latex A makes by example 1.
In 210 parts of latex A (70 parts of solids contents), add 200 parts of water, 0.002 part of ferrous sulfate, 0.004 part of disodium EDTA, 0.1 part of sodium sulfoxylate formaldehyde and 1.8 parts of Repone K.
70 ℃ add 15 parts of vinylbenzene in 5 hours continuously in the gained mixture, the mixture of 15 parts of methyl methacrylates and 0.3 part of cumene hydroperoxide, and repolymerization 1 hour and the graft copolymer latex aqueous solution of median size 1500 .
Make resin combination and, the results are shown in table 1 by example 1 evaluation.
Comparative example 5
Latex is made by example 1.
In the aggregation container that agitator is housed, add 45 parts of latex A (15 parts of solids contents), 200 parts of water, 0.2 part sodium oleate, 0.0017 part of ferrous sulfate, 0.00425 part of disodium EDTA, 0.17 part formaldehyde sulfoxylate sodium salt, 0.17 part Tripotassium phosphate, 63.75 parts of divinyl, 21.25 parts of vinylbenzene, 0.85 part Vinylstyrene and 0.85 part of diisopropylbenzene(DIPB) hydroperoxide, and in 50 ℃ of polymerizations 24 hours.Polymerization began back 6 hours and 12 hours, added 0.3 part of sodium oleate respectively in reaction mixture, and added 0.475 part of sodium oleate in back 18 hours in beginning.Polymer beads median size 1400 in the gained latex (calling " latex B " in the following text), polymerisation conversion 99%.
In 210 parts of latex B (70 parts of solids contents), add 200 parts of water, 0.002 part of ferrous sulfate, 0.004 part of disodium EDTA and 0.1 part of sodium sulfoxylate formaldehyde.Then, 70 ℃ add 14 parts of methyl methacrylates, the mixture of 1.0 parts of vinylbenzene and 0.1 part of cumene hydroperoxide, repolymerization 30 minutes (the first step graft polymerization) in 3 hours continuously in latex.Afterwards, 70 ℃ add 14 parts of vinylbenzene in 3 hours continuously, the mixture of 1.0 parts of methyl methacrylates and 0.2 part of cumene hydroperoxide, and repolymerization 1 hour (the second step graft polymerization) and the graft copolymer latex aqueous solution of median size 1500 .
Make composition and, the results are shown in table 1 by example 1 evaluation.
Comparative example 6
Repeat comparative example 5, just the order of the first step and the second step graft polymerization is turned around.
The results are shown in table 1.
Comparative example 7
Repeat comparative example 3, just potassium chloride dosage is 1.1 parts.
The results are shown in table 1.
Table 1
(continuing)
*
1Whether observe graft copolymer lumps.*
6: M methyl methacrylate Yes: caking; №: do not lump.*
7: B latex B*
2The whether emulsification of used monomer mixture of second step.Ex: the present invention's example Yes: emulsification; №: not emulsification. Com.Ex.: comparative example *
3Scales that produces during graft polymerization and graft copolymer weight ratio.*
4A latex A*
5St vinylbenzene
| Molded PVC composition properties | ||
| Transmittance (%) | Izod shock strength (0 ℃) | |
| Ex.1 Ex.2 Ex.3 Ex.4 | 75 76 69 75 | 21 21 30 21 |
| Com.Ex.1 Com.Ex.2 Com.Ex.3 Com.Ex.4 Com.Ex.5 Com.Ex.6 Com.Ex.7 | 80 79 68 60 69 68 75 | 5 6 15 15 9 9 10 |
Example 5
Latex A makes by example 1.
Add 200 parts of water, 0.002 part of ferrous sulfate, 0.004 part of disodium EDTA, 0.1 part of sodium sulfoxylate formaldehyde and 2.4 parts of Repone K to 210 parts of latex A (70 parts of solids contents).Then, 70 ℃ of mixtures (b ') that in latex, add 4 parts of vinylbenzene and 0.1 part of cumene hydroperoxide in 1 hour continuously, repolymerization 30 minutes (the first step graft polymerization).Afterwards, 70 ℃ in 3 hours with 15 parts of methyl methacrylates, 1.0 the mixture of the mixture (c ') of part vinylbenzene and 0.1 part of cumene hydroperoxide adds in the polyblend of graft polymerization of the first step continuously, and repolymerization 30 minutes (the second step graft polymerization).At last, 70 ℃ add the mixture (d ') of 10 parts of vinylbenzene and 0.2 part of cumene hydroperoxide in the polyblend of the second step graft polymerization in 2 hours continuously, and repolymerization 1 hour (the 3rd step graft polymerization) and the graft copolymer latex aqueous solution.
Graft copolymer latex particle caking back median size 1800 .Scales that produces during graft polymerization and the weight ratio of graft copolymer 4.5%.
Make resin combination and, the results are shown in table 2 by example 1 evaluation.
Example 6
Repeat example 5, the monomer mixture that just is used for the second step graft polymerization, i.e. 15 parts of methyl methacrylates, 1.0 parts of vinylbenzene and 0.1 part of cumene hydroperoxide added the gained emulsion in the reaction mixture of the first step graft polymerization in after the homogenizer emulsification 3 hours in the aqueous solution of 0.3 part of sodium oleate and 15 parts of water continuously.
The results are shown in table 2.
Example 7
Repeating example 5, is that used Repone K amount changes 1.8 parts into, gained graft copolymer median size 1300 .
The results are shown in table 2.
Example 8
Repeat example 5 just before, 15.3 parts of aqueous solution that contain 0.3 part of sodium oleate are added in the first step polymeric reaction mixture monomer mixture (c ').
The results are shown in table 2.
Comparative example 8
Latex A makes by example 1.
In 210 parts of latex A (70 parts of solids contents), add 200 parts of water, 0.002 part of ferrous sulfate, 0.004 part of disodium EDTA and 0.1 part of sodium sulfoxylate formaldehyde.
70 ℃ add 15 parts of methyl methacrylates in 3 hours continuously in the gained mixture, in the mixture of 1.0 parts of vinylbenzene and 0.3 part of cumene hydroperoxide, and repolymerization 30 minutes.
Then, add the mixture of 14 parts of vinylbenzene and 0.2 part of cumene hydroperoxide in 3 hours, and repolymerization 1 hour and the graft copolymer latex aqueous solution of median size 800 .
Make resin combination and, the results are shown in table 1 by example 1 evaluation.
Comparative example 9
Repeat comparative example 8, just the order of the first step and the second step graft polymerization is turned around.
The results are shown in table 2.
Comparative example 10
Repeat comparative example 8, just potassium chloride dosage is 1.8 parts.
The results are shown in table 2.
Comparative example 11
Latex A makes by example 1.
In 210 parts of latex A (70 parts of solids contents), add 200 parts of water, 0.002 part of ferrous sulfate, 0.004 part of disodium EDTA, 0.1 part of sodium sulfoxylate formaldehyde and 2.3 parts of Repone K.
70 ℃ add 15 parts of vinylbenzene in 5 hours continuously in the gained mixture, the mixture of 15 parts of methyl methacrylates and 0.3 part of cumene hydroperoxide, repolymerization 1 hour and the graft copolymer latex aqueous solution of median size 1800 .
Make resin combination and, the results are shown in table 2 by example 1 evaluation.
Comparative example 12
Latex A makes by example 1.
In the aggregation container that agitator is housed, add 27 parts of latex A (9 parts of solids contents), 200 parts of water, 0.2 part sodium oleate, 0.0018 part of ferrous sulfate, 0.0045 part of disodium EDTA, 0.18 part sodium sulfoxylate formaldehyde, 0.18 part Tripotassium phosphate, 68.25 parts of divinyl, 22.75 parts of vinylbenzene, 0.91 part Vinylstyrene and 0.91 part of diisopropylbenzene(DIPB) hydroperoxide, 50 ℃ of polymerizations 40 hours.Polymerization began back 6 hours, after 12 hours and 18 hours, added 0.2635 part of sodium oleate respectively.Polymer beads median size 1650 in the gained latex (calling " latex C " in the following text) polymerisation conversion 99%.
In 210 parts of latex C (70 parts of solids contents), add 200 parts of water, 0.002 part of ferrous sulfate, 0.004 part of disodium EDTA and 0.1 part of sodium sulfoxylate formaldehyde.70 ℃ add 15 parts of methyl methacrylates, the mixture of 1.0 parts of vinylbenzene and 0.1 part of cumene hydroperoxide, repolymerization 30 minutes (the first step graft polymerization) in 3 hours continuously in latex then.Afterwards, 70 ℃ of mixtures that add 14 parts of vinylbenzene and 0.2 part of cumene hydroperoxide in 3 hours continuously, and repolymerization 1 hour (the second step graft polymerization) and the graft copolymer latex aqueous solution of median size 1800 .
Make resin combination and, the results are shown in table 2 by example 1 evaluation.
Comparative example 13
Repeat comparative example 12, just the order of the first step and the second step graft polymerization is turned around.
The results are shown in table 2.
Comparative example 14
Latex C makes by comparative example 12.
In 210 parts of latex (70 parts of solids contents), add 200 parts of water, 0.002 part of ferrous sulfate, 0.004 part of disodium EDTA and 0.1 part of formaldehyde sulfoxylate sodium salt.
70 ℃ of mixtures that in the gained mixture, add 4 parts of vinylbenzene and 0.1 part of cumene hydroperoxide in 1 hour continuously, repolymerization 30 minutes (the first step graft polymerization).
Then, add 15 parts of methyl methacrylates continuously, the mixture of 1.0 parts of vinylbenzene and 0.1 part of cumene hydroperoxide, repolymerization 30 minutes (the second step graft polymerization) in 3 hours.
Afterwards, 70 ℃ of mixtures that add 10 parts of vinylbenzene and 0.2 part of cumene hydroperoxide in 2 hours continuously, and repolymerization 1 hour (the 3rd step graft polymerization) and the graft copolymer latex aqueous solution of median size 1800 .
Make resin combination and, the results are shown in table 2 by example 1 evaluation.
Comparative example 15
Repeat comparative example 10, just potassium chloride dosage changes 1.3 parts into.
The results are shown in table 2.
Table 2
(continuing)
Table 2 is annotated: *
1: add 15.3 parts of aqueous solution that contain 0.3 part of sodium oleate.
| Molded PVC composition properties | ||
| Transmittance (%) | Izod shock strength (0 ℃) | |
| Ex.5 Ex.6 Ex.7 Ex.8 | 67 67 76 67 | 45 45 35 45 |
| Com.Ex.8 Com.Ex.9 Com.Ex.10 Com.Ex.11 Com.Ex.12 Com.Ex.13 Com.Ex.14 Com.Ex.15 | 80 79 67 57 67 65 67 70 | 5 6 25 18 13 20 25 13 |
*
2: C latex C.
The present composition is that shock strength is higher than conventional composition and the also good vinyl chloride resin composition of transparency.
Ingredients listed in example and, certain available other composition and obtain essentially identical result in the listed example of this paper.
Claims (4)
1. vinyl chloride resin composition, it comprises:
(A) 1-30 weight % graft copolymer and
(B) 99-70 weight % vinyl chloride resin;
The preparation of this graft copolymer (A) is
(i) water-soluble ionogen is added in the aqueous latex that contains 50-85 weight parts of butadiene polymkeric substance (a), this polymkeric substance (a) contains 60-100 weight % divinyl, 40-0 weight % aromatic vinyl monomer, 10-0 weight the % vinyl monomer and the 5-0 weight % crosslinkable monomers of copolymerization with it, the median size of this butadiene polymer (a) is less than 0.1 μ m
Subsequently described electrolytical in the presence of the proceed step by step graft polymerization reaction, rubber particle aggegation in described graft polymerization reaction process, wherein said graft polymerization reaction is following to carry out:
(ii) 1-45 weight parts monomers mixture (b) is added in the latex and carries out polymerization,
Monomer mixture (b) comprises 51-100 weight % aromatic vinyl monomer, and 49-0 weight % alkyl methacrylate and 0-20 weight % be the vinyl monomer of copolymerization with it,
(iii) add the monomer mixture (c) of 5-45 weight part in the step polymkeric substance (ii) and carry out polymerization,
Monomer mixture (c) comprises 51-100 weight % alkyl methacrylate, 49-0 weight % aromatic vinyl monomer and 0-20 weight % with it copolymerization vinyl monomer and
(iv) 0-30 weight parts monomers mixture (d) is added in the step polyblend (iii) and carries out polymerization,
This monomer mixture (d) comprises 51-100 weight % aromatic vinyl monomer, and 49-0 weight % alkyl methacrylate and 0-20 weight % be the vinyl monomer of copolymerization with it;
The total amount of polymkeric substance (a), mixture (b), mixture (c) and mixture (d) is 100 weight parts.
2. the composition of claim 1, wherein the amount of butadiene polymer (a) is the 50-85 weight part, the amount of monomer mixture (b) is the 1-20 weight part, the amount of monomer mixture (c) is that the amount of 5-45 weight part and monomer mixture (d) is the 4-30 weight part, and (a) and (b), (c) and total amount (d) are 100 weight parts.
3. the composition of claim 1, wherein the amount of butadiene polymer (a) is the 50-85 weight part, the amount of monomer mixture (b) is the 5-45 weight part, the amount of monomer mixture (c) is that the amount of 5-45 weight part and monomer mixture (d) is 0 weight part, and (a) and (b) and total amount (c) are 100 weight parts.
4. the composition of claim 1, wherein monomer mixture (c) is added to the 5-90 weight part and contains in the aqueous solution of 0.05-3 weight part emulsifying agent, and stirs this mixture and make monomer mixture (c) emulsification, and emulsion is added in the step polymkeric substance (iii) continuously.
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| CN 92103096 CN1052250C (en) | 1992-04-27 | 1992-04-27 | Radio pager having function switches for establishing an additional function of coupling the pager with an external device |
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| CN1046539C (en) * | 1995-04-27 | 1999-11-17 | 中国石化齐鲁石油化工公司 | Synthesis method of polyvinyl chloride impact modifier being butadiene, styrene, methyl methacrylate copolymer |
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