CN101903461A - Composition of styrene based copolymer, polymerization method of said composition, and styrene based copolymer obtained from the method - Google Patents
Composition of styrene based copolymer, polymerization method of said composition, and styrene based copolymer obtained from the method Download PDFInfo
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- CN101903461A CN101903461A CN2007801020227A CN200780102022A CN101903461A CN 101903461 A CN101903461 A CN 101903461A CN 2007801020227 A CN2007801020227 A CN 2007801020227A CN 200780102022 A CN200780102022 A CN 200780102022A CN 101903461 A CN101903461 A CN 101903461A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
Abstract
Provided is a styrene-based copolymer resin composition, a polymerization method of the same composition, and a styrene-based copolymer prepared therefrom. Specifically, the present invention provides a styrene-based copolymer resin composition which is capable of achieving excellent appearance quality, heat resistance and light resistance, a polymerization method of the same composition, and a styrene-based copolymer prepared therefrom.
Description
Technical field
The present invention relates to the polymerization process of styrenic copolymer resin composition, said composition and the styrenic copolymer resin for preparing by this method.More specifically, the present invention relates to obtain excellent exterior quality, thermotolerance and sunproof styrenic copolymer resin composition, the polymerization process of said composition, and by the styrene based copolymer of this method preparation.
Background technology
Generally speaking, conventional styrene resin has the excellent transparency, moldability and rigidity, therefore is widely used as the mold materials that uses in household supplies and household product, electric equipment products and electronic product, packaged material etc.In order further to enlarge the Application Areas of styrene resin, carried out much making great efforts to improve the physical properties of styrene resin or giving styrene resin new function.For example, as stable on heating a kind of method of improving styrene resin, attempt styrene resin and the stable on heating resin (as polyphenylene oxide (polyphenylene oxide), polycarbonate etc.) with excellence are carried out blend.Yet this method exists as painted (coloration), the transparency are low, poor in processability, the high variety of issue of production cost.As another kind of method, attempted by preparation vinylbenzene and can improve the stable on heating method of styrene resin with the copolymer resin composition of styrene copolymerized vinyl compound.
As the example of preparation copolymer resin composition with the stable on heating method of improvement styrene resin, the open flat 11-124461 of No. of Japanese unexamined patent publication No. discloses a kind of method for preparing the multipolymer of vinylbenzene and alpha-methyl styrene.Unfortunately, for example there is following shortcoming in this method: coloring problem, owing to the reactive behavior difference causes the polymerization degree low and cause the mechanical property deficiency owing to molecular weight is low.In addition, the open clear 61-278510 of No. of Japanese unexamined patent publication No. discloses a kind of stable on heating method of improving styrene resin by preparation vinylbenzene-Sipacril 2739OF.Although the vinylbenzene-Sipacril 2739OF that obtains demonstrates significantly improved thermotolerance, but because the actual strength of this vinylbenzene-Sipacril 2739OF is more much lower than the actual strength of styrene resin, therefore the suitability of this vinylbenzene-Sipacril 2739OF is restricted, and this vinylbenzene-Sipacril 2739OF also has (discoloration) problem of fading that produces by being exposed to ultraviolet ray (UV) simultaneously.From business-like viewpoint, when carrying out the successive mass polymerization, owing to the sour condensation of methacrylic acid forms acid anhydrides, this method also has the problem of the exterior quality variation of problem relevant with extrusion method and/or product.The open No.2005-248003 of Japanese unexamined patent publication No. has proposed the terpolymer of preparation vinylbenzene, methacrylic acid and alpha-methyl styrene to improve thermotolerance, and preparation has excellent intensity, the transparency and stable on heating multipolymer thus.Yet still there is painted with product and the photoinduced relevant shortcoming of fading in this method.Owing to forms acid anhydrides by sour condensation when vinylbenzene and methacrylic acid copolymerization, cause the productivity of copolymer resin to hang down problem and shortcoming with appearance poor in order to solve.The flat 9-87332 of the open No. of Japanese unexamined patent publication No. proposes to use 2-Ethylhexyl Alcohol (isooctyl alcohol), and the open No.2006-282962 of Japanese unexamined patent publication No. has then proposed the use n-Octanol.Yet these Japanese Patents also have following problem.Therefore octanol has low boiling temperature, and in the continuous bulk polymerization process of routine, when using two continuous devolatilization equipment, octanol is easy to volatilization.As a result, can not be fully and bring into play octanol inherent function satisfactorily.PCT?WO
The 2007-034789 trial overcomes the problem relevant with sour condensation by the ethylene glycol softening agent that use has ad hoc structure.This method has following shortcoming.That is, employed ethylene glycol softening agent is not easy volatilization in the devolatilization process, but acid anhydrides is demonstrated low reactivity, and is not easy in also therefore that the introducing of ethylene glycol softening agent is the final product of evaporable character.The result is that the introducing of this ethylene glycol will cause extra COLOR FASTNESS PROBLEM in process subsequently.Although above-mentioned patent disclosure suggestion is introduced UV stabilizer in the styrenic copolymer resin composition that obtains, but because behind the described multipolymer of preparation, this method needs other extrusion and is not suitable for the scale operation system, and there is the problem of the increase production cost that is caused by extra manufacturing processed in this method.
Summary of the invention
Therefore, carried out the present invention, the purpose of this invention is to provide and be used to prepare the composition that outward appearance, thermotolerance and photostabilization with excellence keep the styrenic copolymer resin of ideal moldability, the transparency and intensity simultaneously at above problem.
Another object of the present invention provides by the said composition polymerization being prepared the method for styrenic copolymer resin.
Another object of the present invention provides exterior quality, thermotolerance and the sunproof styrenic copolymer resin that obtains by above-mentioned polymerization process and have excellence.
According to an aspect of the present invention, above-mentioned and other purpose can realize that said composition contains by the styrenic copolymer resin composition is provided:
100 weight parts monomers compositions, this monomer composition contain the distyryl compound of 80-99.5 weight % and 0.5-20 weight % can with the vinyl compound of described distyryl compound copolymerization;
The organic solvent of 5-30 weight part; And
0.2-5 the softening agent of weight part.
In one embodiment of the invention, described softening agent can be at least a combination of compounds shown at least a compound shown in the following formula (I) and the following formula (II):
R
1-(-O-CH
2-CH
2-)
n-OH (I)
Wherein, R
1Expression C
1-C
4Replacement or unsubstituted alkyl, and n is the integer of 1-3;
R
2OH (II)
Wherein, R
2Expression C
8-C
30Replacement or unsubstituted alkyl, C
8-C
30Replacement or unsubstituted thiazolinyl or C
8-C
30Cycloalkyl.
In one embodiment of the invention, based on the described monomer composition of 100 weight parts, described composition can also contain the UV stabilizer of 200-3000ppm.
In another embodiment of the invention, described UV stabilizer preferably dimethyl ester is a UV stabilizer.
In another embodiment of the invention, based on the described monomer composition of 100 weight parts, described composition can also contain the initiator of 50-2000ppm.
According to another aspect of the present invention, the invention provides the method for preparing styrenic copolymer resin, this method comprises:
In the tank reactor that successive stirs, introduce the styrenic copolymer resin composition, and carry out polymerization; And
The polymerisate that obtains is transferred in the devolatilizer (devolatilizer), to remove unreacted monomer and organic solvent.
In one embodiment of the invention, preferably will from described devolatilizer, volatilize and the circulate soln of condensation discharging and be transferred to outer tank.
According to another aspect of the present invention, the invention provides the styrenic copolymer resin that obtains by aforesaid method.
Below, the present invention will be described in more detail.
Styrenic copolymer resin composition of the present invention is to prepare by containing distyryl compound and can mix with softening agent with the monomer composition of the vinyl compound of this distyryl compound copolymerization in organic solvent, and styrenic copolymer resin composition of the present invention can also contain UV stabilizer and initiator.This copolymer resin composition can improve exterior quality, thermotolerance and photostabilization, keeps ideal moldability, the transparency and intensity simultaneously.Therefore, in the time of can solving the problem of routine techniques and shortcoming, particularly distyryl compound and vinyl compound copolymerization owing to the problem and the shortcoming that form the product appearance difference that acid anhydrides runs into.In addition, from business-like viewpoint, can advantageously prepare sunproof stable on heating styrenic copolymer resin composition with excellence.Therefore, the styrenic copolymer resin that is obtained by thermotolerance styrenic copolymer resin composition of the present invention demonstrates excellent outward appearance and photostabilization, therefore is highly suitable for comprising the various application of electrical equipment/electronic material and optical material.
The example of the distyryl compound that uses in the described resin combination can include but not limited to vinylbenzene, o-methyl styrene, p-methylstyrene, t-butyl styrene, alpha-methyl styrene and bromostyrene.These materials can use separately or use with their form of arbitrary combination.Vinylbenzene most preferably.
In described monomer composition, can comprise with the example of the vinyl compound of described distyryl compound copolymerization being selected from least a in the group of forming by vinylformic acid, methacrylic acid and toxilic acid, but be not limited thereto.Methacrylic acid preferably.
Based on 100 weight parts contain distyryl compound and can with the monomer composition of the vinyl compound of this distyryl compound copolymerization, described distyryl compound and vinyl compound can use with the ratio of 80-99.5 weight %:0.5-20 weight %, preferred 90-99 weight %:1-10 weight %.If the content of vinyl compound is lower than 0.5 weight % in the described monomer composition, then be difficult to obtain the ideal thermotolerance.On the other hand,, improved thermotolerance if the content of described vinyl compound is higher than 20 weight %, but exist hygroscopic property improve, because significantly the mold pressing difficulty that causes of the viscosity of increase and the shortcoming of fading in time.
The example of the organic solvent that uses in the described resin combination can include but not limited to ethylbenzene, toluene and dimethylbenzene.These organic solvents can use separately or use with their form of combination.Ethylbenzene preferably.The consumption of organic solvent is not particularly limited.For example, based on the described monomer composition of 100 weight parts, preferably use the solvent of 5-30 weight part.If the content of described organic solvent is lower than 5 weight parts, then be difficult to obtain the uniform mixture of each composition.On the other hand, if the content of described organic solvent is higher than 30 weight parts, disadvantageously, will cause reactive the reduction.
For control by can be with the vinyl compound of described distyryl compound copolymerization produce and acid anhydrides that will cause problem, described resin combination can contain the combination of at least a plasticizer compounds shown at least a plasticizer compounds shown in the following formula (I) and the following formula (II):
R
1-(-O-CH
2-CH
2-)
n-OH (I)
Wherein, R
1Expression C
1-C
4Replacement or unsubstituted alkyl, and n is the integer of 1-3;
R
2OH (II)
Wherein, R
2Expression C
8-C
30Replacement or unsubstituted alkyl, C
8-C
30Replacement or unsubstituted thiazolinyl or C
8-C
30Cycloalkyl.
Softening agent with structure shown in the formula (I) has the advantage that obviously is different from conventional acid anhydrides control compound.That is, the softening agent shown in the formula (I) is not volatile in the multipolymer manufacturing processed, and has the ability that can fully control acid anhydrides formation.In addition, this plasticizer compounds does not demonstrate disadvantageous side effect when aftertreatment, because the residual level of described plasticizer compounds in the copolymer resin that obtains is very low.Examples for compounds shown in the formula (I) can include but not limited to: ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol butyl ether etc.In the compound shown in the formula (I), the value of n is 1-3.If the value of n is more than 4, then behind the described resin of preparation, a large amount of softening agent remain in this resin, may extrude with injection process in cause the stable on heating variation of multipolymer and fade.
The example of the plasticizer compounds shown in the formula (II) can include but not limited to: octanol, decyl alcohol, Stearyl alcohol, lauryl alcohol.In the softening agent shown in the formula (II), if carbonatoms is lower than 8, then in the manufacturing processed of described resin, this plasticizer compounds is very easily in volatilization.If carbonatoms is greater than 30, then most of plasticizer compounds that adds remains in the copolymer resin that obtains, and this may cause problem in subsequent process.
Based on the described monomer composition of 100 weight parts, the content of described softening agent can preferably be in the scope of 0.2-5 weight part, more preferably 0.5-3 weight part.If the content of described softening agent is lower than 0.2 weight part, this may cause acid anhydrides control action kou variation.On the other hand, if the content of described softening agent is higher than 5 weight parts, softening agent residual in the copolymer resin that obtains may undesirably cause discoloration of resins, and is combined with the thermotolerance variation.When the softening agent that uses simultaneously shown in softening agent shown in the formula (I) and the formula (II), the content of the softening agent shown in the content of the softening agent shown in the formula (I) and the formula (II) can be 5-50 weight %:95-50 weight % than preferably, more preferably 10-30 weight %:90-70 weight %.If the content of the softening agent shown in the formula (I) is lower than 5 weight %, then may cause acid anhydrides control action kou variation.On the other hand,, then may undesirably cause the extrusion performance variation, and be combined with some problems relevant with discoloration of resins if the content of the softening agent shown in the formula (I) is higher than 50 weight %.
In the continuous bulk polymerization process, the UV stabilizer of using in the described resin combination can be added directly in the reactor.Extensively adopting benzotriazole is the UV stabilizer that stablizer and the conduct of benzophenone series stablizer are used for conventional styrene resin.Yet, in polymerization process these UV stable immunomodulator compounds directly being introduced into the thermostability that can cause described UV stabilizer in the reactor reduces, even guaranteed the ideal thermostability, also can cause extra discoloration of resins, perhaps the problem relevant that causes owing to UV stabilizer inherent color with coloring resin.Owing to these reasons, will introduce an independently compound extrusion with the resin particle bonded UV stabilizer of preparation.Yet, dimethyl ester is that UV stabilizer does not demonstrate because stablizer inherent color and contingent problem, and because dimethyl ester is the outstanding thermostability of UV stabilizer, even in the continuous bulk polymerization process, dimethyl ester is that UV stabilizer still has excellent photostabilization and do not have extra fading.The example of this UV stabilizer is propanedioic acid [(4-methoxyphenyl)-methylene radical] dimethyl ester (by the Hostavin PR-25 of Clariant manufacturing).Based on the described monomer composition of 100 weight parts, the content of UV stabilizer preferably is in the scope of 200-3000ppm (w/w), more preferably 500-1500ppm.If the content of UV stabilizer is lower than 200ppm, the additive effect of UV stabilizer is not obvious.On the other hand, if the content of UV stabilizer is higher than 3000ppm, then may cause the thermotolerance of the copolymer compositions that obtains to reduce and improve production cost.
Based on the described monomer composition of 100 weight parts, described resin combination can also contain initiator.
This initiator can use the initiator of any routine and have no particular limits, as long as can be controlled molecular structure, molecular weight and the polymerization degree.For example, can mention t-butylperoxy-2-ethylhexyl carbonic ether (t-butylperoxy-2-ethylhexylcarbonate) or 2,2-two (4,4-two (t-butylperoxy) cyclohexyl) propane.
Based on the described monomer composition of 100 weight parts, the content of described initiator preferably is in the scope of 50-2000ppm (w/w), more preferably 100-1000ppm.If the content of described initiator is lower than 50ppm, the additive effect deficiency of described initiator then.On the other hand, if the content of described initiator is higher than 2000ppm, then will cause molecular weight to reduce.
Except mentioned component, can in this area, randomly add other material in the conventional acceptable scope, as chain-transfer agent, oxidation inhibitor and thermo-stabilizer.
Use above-mentioned styrenic copolymer resin composition, can prepare copolymer resin as follows.
At first, the described monomer composition of 100 weight parts is mixed with 5-30 weight part organic solvent, as mentioned above, described monomer composition contain the distyryl compound of 80-99.5 weight % and 0.5-20 weight % can with the vinyl compound of described distyryl compound copolymerization, and this mixture is introduced in the tank reactor of two continuously stirring.Based on the described monomer composition of 100 weight parts, in first reactor, add the initiator of 50-2000ppm.Although based on the described monomer composition of 100 weight parts, the softening agent that can be the 0.2-5 weight part with total amount is added in described first reactor, but also the part softening agent can be added directly in the devolatilizer, with the formation of control acid anhydrides in the devolatilization process.Although based on the described monomer composition of 100 weight parts, can be that the UV stabilizer of 200-3000ppm is added in first reactor with total amount, if possible, preferably described softening agent is added directly in the devolatilizer, to avoid thermal history.The polymerization temperature of first reactor is 100-140 ℃, and the polymerization temperature of second reactor is preferably than high 0-15 ℃ of described first reactor.This is because can improve the transformation efficiency that described monomer composition changes polymkeric substance into.If the polymerization temperature of described first reactor is lower than 100 ℃, then will significantly reduce the transformation efficiency that described monomer composition changes polymkeric substance into.In addition, no matter be first reactor or second reactor, the polymerization temperature of reactor all should be no more than 155 ℃.If the polymerization temperature of reactor is higher than 155 ℃, then may causes reacting too fast, and be difficult to control the physical properties of reaction product.Under such reaction conditions, can realize in reactor that the conversion of monomer with 50-70% is a polymkeric substance.
The polymeric polymkeric substance is transferred in the devolatilizer that is connected in series thus then, and unreacted monomer and organic solvent evaporate from reaction soln, isolate polymkeric substance thus.This step is reduced to minimum value with the residual quantity of monomer in the final copolymer rosin products and oligopolymer, improves the thermotolerance and the rigidity of resin thus.The devolatilization process that obtains polymkeric substance is preferably under the vacuum of about 20 holders (Torr), carry out under the high temperature of 200-250 ℃.If the devolatilization process is carried out being lower than under 200 ℃, can not being separated fully of unreacted monomer may cause product thermotolerance variation and painted.If the devolatilization process is carried out being higher than under 250 ℃ the high temperature, softening agent that adds and UV stabilizer be degraded and volatilization easily, therefore can not obtain the ideal copolymer resin composition, and polymer degradation and unnecessary extra reaction can cause obtaining the degraded appearance of polymkeric substance, and be combined with thermotolerance and rigidity reduces.
In examination the product after being exposed to ultraviolet ray is faded may have the factor of influence the time, with distyryl compound in the resin combination of the present invention, can with the discharge of the vinyl compound and the organic solvent of distyryl compound copolymerization, emphasis concentrates on volatilization from devolatilizer, is condensed then and introduced on the circulate soln in the reactor again.Therefore, with the theme of circulate soln as research.
Volatilization in devolatilizer, then be condensed and the composition of being introduced the circulate soln in the reactor again contain distyryl compound, can with vinyl compound, organic solvent, softening agent and other impurity of distyryl compound copolymerization.Particularly, described circulate soln contains greater than the component measured of 95 weight % and is lower than other impurity of 5 weight %, described measure component such as distyryl compound, can with vinyl compound, organic solvent and the softening agent of distyryl compound copolymerization.Described impurity mainly contains just like oligopolymer, high boiling substance (hi-boiler), cumene and the alpha-methyl styrene (composition of α-MS).
When the circulate soln that fades responsive that may cause ultraviolet with UV scanning, show that with UV scanning comparison loop solution (containing impurity) and result with solution (distyryl compound, can with vinyl compound, organic solvent and the softening agent of distyryl compound copolymerization) of the outer identical component of the removal of impurity described circulate soln demonstrates more significant absorption peak at the 280-300nm place.
When described circulate soln carries out circulation time continuously, the concentration of the impurity that contains in the described circulate soln improves, and uses existing commercially available devolatilization system to be difficult to reach and control fully and remove in described circulate soln and increase gradually and cumulative impurity.Cumulative impurity remains in the described resin combination thus, and this may cause variety of issue, as the fading of uv induction, thermotolerance variation, painted etc.According to the present invention, may described circulate soln be introduced into again the photostabilization variation that reactor prevents polymerisate (that is styrenic copolymer resin) in the outer tank by described circulate soln is disposed to.
The styrenic copolymer resin of the present invention that is obtained by said process can improve exterior quality, thermotolerance and the photostabilization of product, moldability, the transparency and the intensity that keeps conventional styrene copolymer resin to demonstrate simultaneously.Therefore, resin of the present invention can be used in and comprises the sheet material extruded and the various application of injection-molded item.
Will describe by following, the invention provides the styrenic copolymer resin composition and method of making the same, this styrenic copolymer resin composition can overcome fully with owing to be exposed to the relevant problem of photostabilization variation that ultraviolet causes and with need not complicated process owing to forming the relevant problem of resin combination degraded appearance that acid anhydrides causes, conventional thermotolerance styrenic copolymer resin composition faces the problems referred to above usually.
The thermotolerance styrenic copolymer resin of the present invention that obtains by above-mentioned composition and method also has improved outward appearance and photostabilization on the stable on heating basis with excellence.Therefore, styrene based copolymer of the present invention can be widely used in the various application that comprise electrical equipment/electronic product and optical articles.
Embodiment
Now, will the present invention be described in more detail with reference to the following example.These embodiment only are provided for the purpose of illustrating the invention, limit the scope of the invention and essence and should not be regarded as.
Embodiment 1
90 parts by weight of styrene (SM) and 10 weight part methacrylic acids (MAA) are mixed, with the preparation monomer composition.In 100 weight parts monomers compositions, add 14 weight part ethylbenzene, 4 weight part 2-Ethylhexyl Alcohols, 1 weight part diethylene glycol monobutyl ether, 200ppm propanedioic acid [(4-methoxyphenyl)-methylene radical] dimethyl ester (by the Hostavin PR-25 of Clariant manufacturing) and 100ppm 2,2-two (4,4-two (t-butylperoxy) cyclohexyl) propane (available from the Pertetra-A of the NOF Corporation of Japan).The reaction mixture that will prepare is thus introduced first reactor then, carries out polymerization subsequently.The temperature that is added with first reactor of described composition is set at 135 ℃, the temperature of second reactor is set at 140 ℃, and residence time of reactant is adjusted to make final transformation efficiency be 60%.Then, the reaction mixture that obtains is transferred in the continuous devolatilizer, then this devolatilizer is warming up to 240 ℃, extrude continuously subsequently, thereby prepare granular styrene resin, under the vacuum of 20 holders, remove volatiles simultaneously.By the circulate soln that will from described devolatilizer, volatilize and be discharged into outer tank and this solution do not returned and is circulated to reactor, fundamentally stop circulate soln to participate in reaction.
Embodiment 2
Prepare granular copolymer resin in the mode identical, except adding 2 weight part 2-Ethylhexyl Alcohols and 3 weight part diethylene glycol monobutyl ethers as softening agent with embodiment 1.
Embodiment 3
Prepare granular copolymer resin in the mode identical, except adding 1.5 weight part 2-Ethylhexyl Alcohols and 0.5 weight part diethylene glycol monobutyl ether as softening agent with embodiment 1.
Embodiment 4
85 parts by weight of styrene (SM) and 15 weight part methacrylic acids (MAA) are mixed, with the preparation monomer composition.In the described monomer composition of 100 weight parts, add 20 weight part ethylbenzene, 4 weight part 2-Ethylhexyl Alcohols, 1 weight part diethylene glycol monobutyl ether and 200ppm propanedioic acid [(4-methoxyphenyl)-methylene radical] dimethyl ester (by the Hostavin PR-25 of Clariant manufacturing).The reaction mixture that obtains is thus introduced in the reactor that is connected in series, and prepared granular copolymer resin in the mode identical with embodiment 1.
Embodiment 5
94 parts by weight of styrene (SM) and 6 weight part methacrylic acids (MAA) are mixed, with the preparation monomer composition.In the described monomer composition of 100 weight parts, add 12 weight part ethylbenzene, 2 weight part 2-Ethylhexyl Alcohols, 1 weight part diethylene glycol monobutyl ether, 200ppm propanedioic acid [(4-methoxyphenyl)-methylene radical] dimethyl ester (by the Hostavin PR-25 of Clariant manufacturing) and 100ppm 2,2-two (4,4-two (t-butylperoxy) cyclohexyl) propane (available from the Pertetra-A of Japanese NOF Corporation).According to the mode identical, use the reaction mixture of preparation thus to prepare granular copolymer resin with embodiment 1.
Embodiment 6
Prepare granular copolymer resin in the mode identical, except adding 700ppm propanedioic acid [(4-methoxyphenyl)-methylene radical] dimethyl ester (the Hostavin PR-25 that makes by Clariant) as the UV stabilizer that is used for copolymer resin composition with embodiment 2.
Embodiment 7
Prepare granular copolymer resin in the mode identical, except adding 1500ppm propanedioic acid [(4-methoxyphenyl)-methylene radical] dimethyl ester (HostavinPR-25 that makes by Clariant) as the UV stabilizer that is used for copolymer resin composition with embodiment 2.
Comparative example 1
Prepare granular copolymer resin in the mode identical with embodiment 1, except 75 parts by weight of styrene (SM) and 25 weight part methacrylic acids (MAA) are mixed, with the preparation monomer composition, and 20 weight part ethylbenzene and 4 weight part 2-Ethylhexyl Alcohols are added in the 100 weight parts monomers compositions.
Comparative example 2
Prepare spherical copolymer resin in the mode identical with embodiment 1, the softening agent that is used for copolymer resin composition except the diethylene glycol monobutyl ether conduct of adding 0.2 weight part 2-Ethylhexyl Alcohol and 0.2 weight part, and do not use as 2 of initiator, 2-two (4,4-two (t-butylperoxy) cyclohexyl) propane (available from the Pertetra-A of Japanese NOF Corporation).
Comparative example 3
Prepare granular copolymer resin in the mode identical, except only using 4 weight part 2-Ethylhexyl Alcohols as the softening agent that is used for copolymer resin composition with embodiment 1.
Comparative example 4
Prepare granular copolymer resin in the mode identical, except only using 3 weight part diethylene glycol monobutyl ethers as the softening agent that is used for copolymer resin composition with embodiment 1.
Comparative example 5
Prepare granular copolymer resin in the mode identical, except in copolymer resin composition, not adding propanedioic acid as UV stabilizer (HostavinPR-25 that makes by Clariant) with embodiment 2.
Comparative example 6
Prepare granular copolymer resin in the mode identical, except in copolymer resin composition, adding 100ppm propanedioic acid (the Hostavin PR-25 that makes by Clariant) as UV stabilizer with embodiment 2.
Comparative example 7
Prepare granular copolymer resin in the mode identical, except reclaim and use the circulate soln of evaporable 50% from devolatilizer by the formulations prepared from solutions device with embodiment 2.
Comparative example 8
Prepare granular copolymer resin in the mode identical, except reclaim and use the circulate soln of evaporable 100% from devolatilizer by the formulations prepared from solutions device with embodiment 2.
Comparative example 9
Prepare granular copolymer resin in the mode identical with embodiment 2, except will be from devolatilizer the circulate soln of evaporable 100% reclaim and be circulated to reactor, and in copolymer resin composition, do not add propanedioic acid as UV stabilizer (HostavinPR-25 that makes by Clariant).
The evaluation of outward appearance
The melt fracture phenomenon that occurs in the extrusion during by the preparation multipolymer detects the effect by the acid anhydrides that can produce with the vinyl compound of distyryl compound copolymerization.In addition, (width: size is greater than the quantity of the apparent gel impurity of 300 μ m 0.1m) for thickness: 1mm, length: 1m for the sheet extrudate of the copolymer resin that obtains among detection embodiment 1-7 and the comparative example 1-9.
The mensuration of impurity
The particle of 0.2g embodiment 1-7 and comparative example 1-8 acquisition is dissolved in the 5mL methylene dichloride, adds 5mL methyl alcohol then.Filter sedimentary thus polymkeric substance, use efficient (HP) gas-chromatography 5890 series (Hewlett Packard) to analyze filtrate.Major impurity that the main substance of being measured comprises such as oligopolymer, high boiling substance, cumene and alpha-methyl styrene.The mensuration of residual monomer for reference only.
Sunproof mensuration
(Δ YI) estimates photostabilization according to aberration.For this purpose, the particle with embodiment 1-7 and comparative example 1-9 acquisition is processed into the injected sample that thickness is 2mm under 230 ℃.Then, 230 ℃ use down color difference meters (ZE 2000, Nippon Denshoku, Japan) to sample carry out 500 hours UV-con (QUV, Q-Lab Corp., USA).Be determined at the YI poor (Δ YI) that sample is carried out 500 hours by a definite date test front and back.
Measure dimension card (Vicat) softening temperature
The particle of embodiment 1-7 and comparative example 1-9 acquisition is processed into the injected sample that thickness is 3.2mm under 230 ℃, and uses heat distortion test machine (148HD-PC, YASUDA, Japan) to measure vicat softening temperature according to ASTM D 1525 (A/50).
The composition of embodiment 1-7 and test result provide in following table 1.
Table 1
| Form | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 |
| Vinylbenzene (weight percent (pbw)) | 90 | 90 | 90 | 85 | 94 | 90 | 90 |
| Methacrylic acid (weight percent) | 10 | 10 | 10 | 15 | 6 | 10 | 10 |
| Ethylbenzene (weight percent) | 14 | 14 | 14 | 20 | 12 | 14 | 14 |
| 2-Ethylhexyl Alcohol (weight percent) | 4 | 2 | 1.5 | 4 | 2 | 2 | 2 |
| Diethylene glycol monobutyl ether (weight percent) | 1 | 3 | 0.5 | 1 | 1 | 3 | 3 |
| UV stabilizer (ppm) | 200 | 200 | 200 | 200 | 200 | 700 | 1500 |
| Polymerization starter (ppm) | 100 | 100 | 100 | 0 | 100 | 100 | 100 |
| Employed circulate soln (%) | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| Vicat softening temperature (℃) | 123.3 | 124.4 | 124.1 | 129.7 | 119.6 | 123.7 | 122.8 |
| Outward appearance (number of gels) | 8 | 3 | 15 | 18 | 7 | 4 | 5 |
| ΔYI | 4.6 | 4.9 | 4.1 | 5.1 | 3.8 | 3.1 | 2.5 |
| Impurity (%) | 0.4 | 0.5 | 0.3 | 0.5 | 0.4 | 0.5 | 0.6 |
* the consumption of circulate soln: the per-cent (%) of circulate soln that is circulated to the recovery of reactor.
* the proportion of composing of circulate soln is controlled to be and contains 58-60 parts by weight of styrene, 0.5-1.5 weight part methacrylic acid, 34-36 weight part ethylbenzene, 0.5-1 weight part softening agent and 3-4 weight part impurity.
* polymerization starter: 2,2-two (4,4-two (t-butylperoxy) cyclohexyl) propane (available from the Pertetra-A of Japanese NOFCorporation).
* UV stabilizer: propanedioic acid [(4-methoxyphenyl)-methylene radical] dimethyl ester (the Hostavin PR-25 that makes by Clariant).
The composition of comparative example 1-9 and test result provide in following table 2.
Table 2
| Form | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 | Comparative example 9 |
| Vinylbenzene (weight percent) | 75 | 90 | 90 | 90 | 90 | 90 | 90 | 90 | 90 |
| Methacrylic acid (weight percent) | 25 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 |
| Ethylbenzene (weight percent) | 20 | 14 | 14 | 14 | 14 | 14 | 14 | 14 | 14 |
| 2-Ethylhexyl Alcohol (weight percent) | 4 | 0.2 | 4 | 0 | 2 | 2 | 2 | 2 | 2 |
| Diethylene glycol monobutyl ether (weight percent) | 1 | 0.2 | 0 | 3 | 3 | 3 | 3 | 3 | 3 |
| UV stabilizer (ppm) | 200 | 200 | 200 | 200 | 0 | 100 | 200 | 200 | 0 |
| Polymerization starter (ppm) | 100 | 0 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| The circulate soln (%) that uses | 0 | 0 | 0 | 0 | 0 | 0 | 50 | 100 | 100 |
| Vicat softening temperature (℃) | Do not analyze (NA) | Do not analyze | 124.1 | 124.5 | 125.3 | 124.9 | 123.9 | 123.7 | 124 |
| Outward appearance (number of gels) | Melt fracture | Melt fracture | 37 | 25 | 5 | 5 | 7 | 6 | 7 |
| ΔYI | Do not analyze | Do not analyze | 4.9 | 4.5 | 8.9 | 7.4 | 6.8 | 7.9 | 11.6 |
| Impurity (%) | Do not analyze | Do not analyze | 0.4 | 0.5 | 0.5 | 0.5 | 0.8 | 1.1 | 1.2 |
* the consumption of circulate soln: the per-cent (%) of circulate soln that is circulated to the recovery of reactor.
* polymerization starter: 2,2-two (4,4-two (t-butylperoxy) cyclohexyl) propane (available from the Pertetra-A of Japanese NOFCorporation).
* UV stabilizer: propanedioic acid [(4-methoxyphenyl)-methylene radical] dimethyl ester (the Hostavin PR-25 that makes by Clariant).
* the proportion of composing of circulate soln is controlled to be and contains 58-60 parts by weight of styrene, 0.5-1.5 weight part methacrylic acid, 34-36 weight part ethylbenzene, 0.5-1 weight part softening agent and 3-4 weight part impurity.
From the result of table 1 and table 2 as can be seen, when preparation styrenic copolymer resin composition of the present invention, combination by using two kinds of different softening agent and UV stabilizer and in conjunction with circulate soln is discharged into the outside can obtain to have excellent outward appearance and sunproof heat-resistant copolymerized resin composition.
Claims (8)
1. styrenic copolymer resin composition, this styrenic copolymer resin composition contains:
100 weight parts monomers compositions, this monomer composition contain the distyryl compound of 80-99.5 weight % and 0.5-20 weight % can with the vinyl compound of described distyryl compound copolymerization;
5-30 weight part organic solvent; And
0.2-5 weight part softening agent.
2. styrenic copolymer resin composition according to claim 1, wherein, described softening agent is at least a combination of compounds shown at least a compound shown in the following formula (I) and the following formula (II):
R
1-(-O-CH
2-CH
2-)
n-OH (I)
Wherein, R
1Expression C
1-C
4Replacement or unsubstituted alkyl, and n is the integer of 1-3;
R
2OH (II)
Wherein, R
2Expression C
8-C
30Replacement or unsubstituted alkyl, C
8-C
30Replacement or unsubstituted thiazolinyl or C
8-C
30Cycloalkyl.
3. styrenic copolymer resin composition according to claim 1, wherein, based on the described monomer composition of 100 weight parts, this styrenic copolymer resin composition also contains the UV stabilizer of 200-3000ppm.
4. styrenic copolymer resin composition according to claim 3, wherein, described UV stabilizer is that dimethyl ester is a UV stabilizer.
5. method for preparing styrenic copolymer resin, this method comprises:
In the tank reactor of continuously stirring, introduce any described styrenic copolymer resin composition among the claim 1-4, and carry out polymerization; And
The polymerisate that obtains is transferred in the devolatilizer, to remove unreacted monomer and organic solvent.
6. method according to claim 5, wherein, the circulate soln discharging of the also condensation of will volatilizing from described devolatilizer also is transferred to outer tank.
7. the styrenic copolymer resin that obtains by claim 5 or 6 described methods.
8. the moulded product that uses the described styrenic copolymer resin of claim 7 to obtain.
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| KR1020070135428A KR100896946B1 (en) | 2007-12-21 | 2007-12-21 | Composition of styrene based copolymer, polymerization method of said composition, and styrene based copolymer obtained from the method |
| KR10-2007-0135428 | 2007-12-21 | ||
| PCT/KR2007/006866 WO2009082047A1 (en) | 2007-12-21 | 2007-12-27 | Composition of styrene based copolymer, polymerization method of said composition, and styrene based copolymer obtained from the method |
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| US4195169A (en) | 1977-09-13 | 1980-03-25 | The Dow Chemical Company | Devolatilizing polymers of styrene and acrylic or methacrylic acid |
| GB2261663B (en) * | 1991-11-15 | 1996-04-24 | Asahi Chemical Ind | Binder and vehicle compositions comprising a neutralized polysaccharide derivative |
| JPH0867761A (en) * | 1994-08-30 | 1996-03-12 | Dainippon Ink & Chem Inc | Production of expandable styrene resin granule |
| KR100255068B1 (en) * | 1995-03-03 | 2000-05-01 | 야마모토 카즈모토 | Flame retardant for styrene resin and composition |
| JP5008254B2 (en) * | 2004-11-15 | 2012-08-22 | Ｐｓジャパン株式会社 | Styrene copolymer resin composition, heat-resistant extruded foam sheet and container |
| JP2006282962A (en) * | 2005-04-05 | 2006-10-19 | Toyo Styrene Co Ltd | Aromatic vinyl compound-methacrylic acid-based copolymer and method for producing the same |
| JP5237640B2 (en) * | 2005-09-20 | 2013-07-17 | 東洋スチレン株式会社 | Aromatic vinyl compound- (meth) acrylic acid copolymer resin-containing composition and method for producing the same |
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