CN1074223A - The synthetic method of polystyrene with super-high molecular weight - Google Patents
The synthetic method of polystyrene with super-high molecular weight Download PDFInfo
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- CN1074223A CN1074223A CN 92100199 CN92100199A CN1074223A CN 1074223 A CN1074223 A CN 1074223A CN 92100199 CN92100199 CN 92100199 CN 92100199 A CN92100199 A CN 92100199A CN 1074223 A CN1074223 A CN 1074223A
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- molecular weight
- high molecular
- polystyrene
- polysubstituted
- initiator
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and 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
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/06—Hydrocarbons
- C08F12/08—Styrene
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
With polysubstituted bibenzyl compound is carbon-to-carbon of bonding initiator, synthesizes Mw 40 * 10 with substance law, bulk solution method, suspension method and emulsion method
4Above polystyrene with super-high molecular weight.Shock strength, flexural strength and the thermal stability of polystyrene have been increased substantially.
Description
The invention belongs to the synthetic method of polystyrene with super-high molecular weight in the chemical industry production field.
(weight-average molecular weight Mw is 4 * 10 to polystyrene with super-high molecular weight
4More than) synthetic be one of the important development direction of p-poly-phenyl ethene (PS) modification in polymer chemistry and the chemical industry.
Before the present invention, the synthetic method of relevant ultra-high molecular weight PS, all there are patent or paper report in countries such as Japan, the Soviet Union, the U.S..Soviet Union Antipova, A.M. etc.
(1)Adopting the Ti-Al-Mg complex compound is catalyzer; Japan Sumitimo Chemical Co.Ltd.
(2)Adopt superoxide and PhCH
2NH
2System is an initiator; Mitsubishi Rayon Co., Ltd
(3)Adopt superoxide and FeSO
4Oxidation-reduction system, and Kotani Teizo etc.
(4)Also adopt superoxide and amine system to cause styrene polymerization, in order to the polystyrene with super-high molecular weight of synthesis of narrow distribution.The initiator system that above document adopts is all very complicated, introduces more impurity in product.Except that the present invention, polysubstituted bibenzyl carbon-to-carbon of bonding initiator also of no use so far causes the bibliographical information that vinylbenzene is produced polystyrene with super-high molecular weight.
As follows with the main existing reference of the same technical field of invention place:
[1]Antipova，A.M.;Morozova，T.K.;Gaponik，L.V.;Mordykin，V.P.Vysokomol.Soedin.，Ser.B 1986，28（3），182-5.
[2]Sumitomo Chemical Co.，Ltd.Jpn.Kokai Tokkyo Koho JP 82，117，505（Cl.C08F4/40），22 Jul 1982，Appl.81/3，661，12 Jan 1981.
[3]Mitsubishi Rayon Co.，Ltd.Jpn.Kokai Tokkyo Koho JP 82 47，703（Cl.C08F2/22），10 Mar 1982，Appl.80/119，094，29 Aug 1980.
[4]Kotani，Teizo;Inoue，Takashi;Arai，Kozo Japan.Kokai 77 84，269（Cl.C084/40），13 Jul 1977，Appl.76/297，01 Jan 1976.
[5]1L Hyun Park，Lewis Fetters，and Benjamin Chu Macromolecules 1988，21（4），1178-80.
[6]Gao.Y.S.Macromolecules 1985，18（6），1272-7.
[7]Plazek，D.J.Rheol.，[Proc.Int.Congr.]8th 1980，2，493-8.
The method of existing synthetic ordinary polystyrene is difficult to obtain polystyrene with super-high molecular weight. Although the anionic polymerization method can make polystyrene with super-high molecular weight, owing to require low temperature and a large amount of solvent, so be mainly used in the polystyrene standards of synthesis of narrow molecular weight distribution, be difficult for realizing industrialization.
The objective of the invention is with lower production cost synthetic polystyrene with super-high molecular weight with good use properties.These use propertieies comprise thermal characteristics, mechanical property (shock strength and flexural strength), the transparency, electrical property.
The present invention adopts as the represented polysubstituted bibenzyl compound of (1) formula is initiator (being called carbon-to-carbon of bonding initiator), cause styrene monomer with substance law, bulk solution method, suspension method or emulsion method, carry out the radical addition polymerization reaction, the synthesizing super high molecular weight polystyrene.
R
1=RO, R, Cl, H(R=alkyl)
R
2=CN, C
6H
5, CO
2The R(R=alkyl)
R
3=CO
2R, CONH
2, CONHR, COR, OR, R(R=alkyl)
(1) substance law
Under 40～120 ℃ temperature condition; in the container of protection of inert gas; adding the polysubstituted bibenzyl compound of 0.05～2.0g with every 100g vinylbenzene is initiator; as 2; 3-dicyano-2; 3-two (P-p-methoxy-phenyl) diethyl succinate, polyreaction 20～100 hours, obtaining Mw is 40 * 10
4～300 * 10
4, dispersion coefficient D is 3.5～7.0, transmittance 89%, and shock strength is that 17.9～38.4J/m flexural strength is 86.8～110.5MPa, tensile strength is the polystyrene with super-high molecular weight of 43.1～63.3MPa.
(2) bulk solution method
In the container that mechanical stirring, inert gas conduit and thermometer are housed, adding the polysubstituted biphenyl compound of 0.05～2.0g with every 100g vinylbenzene is initiator, as 2, and 3-dicyano-2,3-two (P-p-methoxy-phenyl) diethyl succinate, and 1～20g ethylbenzene, keep temperature of reaction at 40～120 ℃, reacted 5～60 hours, when the commentaries on classics ratio is 40～70%, slough unreacted monomer and ethylbenzene, get the water white transparency polystyrene, Mw is 90 * 10
4～110 * 10
4, dispersion coefficient D is 4～7.
(3) suspension method
In the 100L reactor, add entry 70～30kg successively, Natvosol 0.01～1kg, NaPO
410H
2O 0.001～1kg, after stirring, adding to be dissolved with the polysubstituted bibenzyl compound of 0.05～2.0g in every 100g vinylbenzene again is initiator, as 2, the solution of 3-dicyano-2,3 two (P-p-methoxy-phenyl) diethyl succinate, 30～120 ℃ of reactions 5～80 hours, after routine is handled, get transparent pearl polystyrene, Mw is 50.6 * 10
4, D is 3.
(4) emulsion method
Be equipped with in the appropriate reaction container of agitator, protection of inert gas one; add entry 100～300g, NaOH0.01～1g, sodium laurylsulfonate 0.01～3g; after being heated to 30～120 ℃; adding to be dissolved with the polysubstituted bibenzyl compound of 0.05～2.0g in every 100g vinylbenzene again is initiator, as 2, and 3-dicyano-2; the solution of 3-two (P-p-methoxy-phenyl) diethyl succinate; and 0.5～10g polyoxyethylene glycol, keep 30～120 ℃ of temperature of reaction, polyreaction 5～80 hours.
The obtained polystyrene with super-high molecular weight of the present invention, Mw are 40 * 10
4～300 * 10
4, D is 3～8.Measured data shows, compares with ordinary polystyrene, and thermal stability, shock strength and flexural strength all are significantly improved, and keeps the transparency, and production cost is lower.
The present invention has an embodiment as follows:
In the thermostat that mechanical stirring, thermostat are housed, add suitable quantity of water, heating makes and reaches 60 ℃, keeps constant temperature.With 0.1g 2,3-dicyano-2,3-two (P-p-methoxy-phenyl) diethyl succinate are dissolved in the 100 gram vinylbenzene (polymerization-grade), are sub-packed in the 150ml tube sealing of crossing with inert gas replacement, and sealing is placed in the thermostat, and picks up counting.Constant temperature keeps taking out after 50 hours, and room temperature to be chilled to is cut tube sealing and got the water white transparency polystyrene, pulverizes back test thermomechanical property and electrical property.
Improving the homopolymer molecular weight is one of developing direction of polymer modification.The present invention is an initiator with polysubstituted bibenzyl compound, causes the vinylbenzene homopolymerization with substance law, bulk solution method, suspension method or emulsion method, all makes the water white transparency polystyrene with super-high molecular weight, and according to different condition, Mw is 40 * 10
4～300 * 10
4, D is 3～8, has increased substantially shock strength and the flexural strength of PS, thermal stability and transmittance also all increase, but increase production cost hardly.
Claims (5)
1, the method for synthesizing super high molecular weight polystyrene is characterized in that: adopting polysubstituted bibenzyl compound is carbon-to-carbon type initiator, with substance law, bulk solution method, emulsion method and suspension method synthesizing super high molecular weight polystyrene.
2, a kind of method by the determined synthesizing super high molecular weight polystyrene of claim 1; said substance law; it is characterized in that: under 40～120 ℃ temperature condition; in the container of protection of inert gas; to add the polysubstituted bibenzyl compound of 0.05～2.0g in per 100 gram vinylbenzene is initiator, polyreaction 20～100 hours.
3, a kind of method by the determined synthesizing super high molecular weight polystyrene of claim 1; said bulk solution method; it is characterized in that: in the container of a protection of inert gas; to add the polysubstituted bibenzyl compound of 0.05～2.0g in per 100 gram vinylbenzene is initiator; and the ethylbenzene of 1～20g; keep temperature of reaction at 40～120 ℃, reacted 5～60 hours.
4, a kind of method by the determined synthesizing super high molecular weight polystyrene of claim 1, said suspension method is characterized in that: in a suitable reaction vessel, add entry 70～30kg, Natvosol 0.01～1kg, NaPO
410H
2O 0.001～1kg, after stirring, the solution that to add to be dissolved with the polysubstituted bibenzyl compound of 0.05～2.0g in every 100g vinylbenzene again be initiator was 30～120 ℃ of reactions 5～80 hours.
5, a kind of method by the determined synthesizing super high molecular weight polystyrene of claim 1; said emulsion method; it is characterized in that: in the appropriate reaction container of a protection of inert gas; add entry 100～300g; NaOH0.01～1g; sodium laurylsulfonate 0.01～3g; after being heated to 30～120 ℃; the solution that to add to be dissolved with the polysubstituted bibenzyl compound of 0.05～2.0g in every 100g vinylbenzene again be initiator; and 0.5～10g polyoxyethylene glycol; keep 30～120 ℃ of temperature of reaction, polyreaction 5～80 hours.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92100199 CN1032542C (en) | 1992-01-10 | 1992-01-10 | Synthetic method for polystyrene with super-high molecular weight |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92100199 CN1032542C (en) | 1992-01-10 | 1992-01-10 | Synthetic method for polystyrene with super-high molecular weight |
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| Publication Number | Publication Date |
|---|---|
| CN1074223A true CN1074223A (en) | 1993-07-14 |
| CN1032542C CN1032542C (en) | 1996-08-14 |
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|---|---|---|---|
| CN 92100199 Expired - Fee Related CN1032542C (en) | 1992-01-10 | 1992-01-10 | Synthetic method for polystyrene with super-high molecular weight |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103772533A (en) * | 2013-12-25 | 2014-05-07 | 北京化工大学 | Initiator, preparation method and application |
| CN104628922A (en) * | 2014-09-30 | 2015-05-20 | 青岛科技大学 | Preparation method of ultra-high molecular weight polystyrene used for selective laser sintering rapid formation |
| CN106674390A (en) * | 2016-12-30 | 2017-05-17 | 常州大学 | Method for preparing ultra-high molecular weight polystyrene under room temperature through emulsion polymerization |
-
1992
- 1992-01-10 CN CN 92100199 patent/CN1032542C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103772533A (en) * | 2013-12-25 | 2014-05-07 | 北京化工大学 | Initiator, preparation method and application |
| CN103772533B (en) * | 2013-12-25 | 2016-07-06 | 北京化工大学 | A kind of initiator, preparation method and application |
| CN104628922A (en) * | 2014-09-30 | 2015-05-20 | 青岛科技大学 | Preparation method of ultra-high molecular weight polystyrene used for selective laser sintering rapid formation |
| CN106674390A (en) * | 2016-12-30 | 2017-05-17 | 常州大学 | Method for preparing ultra-high molecular weight polystyrene under room temperature through emulsion polymerization |
| CN106674390B (en) * | 2016-12-30 | 2019-05-28 | 常州大学 | The method that emulsion polymerization room temperature prepares polystyrene with super-high molecular weight |
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| Publication number | Publication date |
|---|---|
| CN1032542C (en) | 1996-08-14 |
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