CN1204653A - Synthesis technology for active cation thermoplastic elastic body - Google Patents
Synthesis technology for active cation thermoplastic elastic body Download PDFInfo
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- CN1204653A CN1204653A CN 98102283 CN98102283A CN1204653A CN 1204653 A CN1204653 A CN 1204653A CN 98102283 CN98102283 CN 98102283 CN 98102283 A CN98102283 A CN 98102283A CN 1204653 A CN1204653 A CN 1204653A
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Abstract
A process for synthesizing thermoplastic polyolefine elastomer includes preparing the soft segment of synthetic active cationic polyisobutylene rubber from mixed solvent, trigger, cotrigger, nucleophile and soft segment monomer at low temp and normal pressure under the protection of dry nitrogen gas, and adding blocking agent, plastic hard segment monomer and end stopper to obtain thermoplastic block elastomer with a molecular weight range of 7000-95000 and a molecular weight distribution of 1.26-1.44. Its advantages are narrow molecular weight distribution and excellent properties.
Description
The present invention relates to the synthesis technique of the known macromolecular compound of a class, more particularly, the present invention relates to the new synthesis technique of a class Thermoplastic Elastomer, Olefinic.
Thermoplastic elastomer can carry out melt-processed as thermoplastics again owing to performance classes under the room temperature is similar to vulcanized rubber, satisfies people's some particular requirement to material property and processing aspect, develops rapider.
With the polymerization technique of active cation, the synthesis technique of preparation polyisobutene thermoplastic elastomer provides a kind of end-capping reagent synthetic segmented copolymer method of utilizing as the WO95/10554 patent, with tert-butyl-dicumyl chlorine and three cumyl chlorine, with TiCl at present
4Be initiator system, methyl chloride and Hx are mixed solvent with 40: 60 (V/V); At-80 ℃ of living polymerizations that carry out iso-butylene, add end-capping reagent 1.1-diphenylethlene thereafter, add different third oxygen acid phthalein again, add p-methylstyrene at last, the triblock copolymer of synthetic poly-p-methylstyrene-polyisobutene-poly-p-methylstyrene, it is soft section of rubber that the WO91/11468 patent provides with the polyisobutene, serves as the method for the thermoplastic elastomer of hard section with vinylbenzene, indenes or both derivatives, with dicumyl ether or three cumyl ether and TiCl
4Be initiator system, above method gained block polymer molecular weight distribution broad, physicals is poor, and on block polymer synthesis, the character that relates to thermoplastic elastomer is few.
The objective of the invention is to avoid above-mentioned weak point of the prior art, and provide a kind of Thermoplastic Elastomer, Olefinic new synthesis technique, make narrower, the excellent performance of product molecular weight distribution, it is more to relate to thermoplastic elastomer.
Purpose of the present invention can reach by following measure, under normal pressure, and temperature of reaction 0～-90 ℃, under the exsiccant nitrogen protection, form by following several steps successively:
(1) mixed solvent; Initiator: a kind of compound or its mixture with following general formula
R wherein
1, R
2Represent hydrogen atom separately, R
1, R
2, R
3Represent C separately
1～C
8The straight or branched alkyl, R
2Represent five yuan, hexa-atomic saturated or unsaturated ring, R
1And R
2Form five yuan, hexa-atomic saturated or unsaturated ring, X representation hydroxy, ether, ester group, halogen with the carbon atom that links to each other together; The coinitiator Lewis acid; The nucleophilic reagent Lewis base, first ageing 10～60 minutes adds isobutylene monomer, makes soft section of active cation polyisobutylene synthetic rubber;
(2) thereafter, add end-capping reagent 1 or benzophenone, ageing added the plastic hard section monomer after 15 minutes, and just the two ends of soft section of polyisobutylene synthetic rubber connect hard section of synthetic plastics;
(3) terminator is collected product from reaction mixture.
Gained block polymer molecular weight product is between 70000～95000, and molecular weight distribution is between 1.26～1.44.
The monomer that rubber is soft section is an iso-butylene, and the monomer of plastic hard section is the organic compound that contains vinyl, can be the compound of aliphatics, aromatic series, alicyclic ring class, as vinylbenzene, indenes, vinyl toluene etc.
Mixed solvent is CH
3Cl or CH
2Cl
2, to mix with any hexane in hexanaphthene, normal hexane, the methylcyclohexane, its volume ratio is the mixed solvent of 40: 60 (V/V) preparation, preferable mixed solvent is CH
3Cl: the mixed solvent of hexanaphthene=40: 60 (V/V).
Initiator mainly is the compound that contains tertiary carbon, can be alcohol, ether, ester, Organohalogen compounds or mixture, as to dicumyl chlorine, dicumyl methyl ether, 2,4,4-trimethylammonium-2-chloropentane (TMPCl), 2-chloro-2-phenyl-propane, 1,3,5-three (2-chloropropyl) benzene, 1-phenyl vinyl chlorine, three cumyl methyl ethers, terephthalic acid methyl esters etc., preferable initiator is to dicumyl chlorine and terephthalic acid methyl esters.
The coinitiator Lewis acid is SnCl
4, BCl
3, TiCl
4, SbF
5, SeCl
3, ZnCl
2, FeCl
3, VCl
4, AlRnCl
3-n, wherein R represents C
1～C
8The straight or branched alkyl, n represents 0～3 integer, preferable coinitiator is TiCl
4
Nucleophilic reagent (claim the proton capture agent again, or electron donor) Lewis base is the hexahydropyridine or derivatives thereof, fatty amine, aromatic amine; Preferable nucleophilic reagent is a hexahydropyridine.
End-capping reagent is the compound that can form metastable carbonium ion, can be 1, benzophenone, and α-methoxy styrene, 1-isopropyl naphthalene etc., preferable end-capping reagent is 1 and benzophenone.
Terminator: methyl alcohol or alcoholic acid hydrochloric acid soln.
Volume with solvent is 1L, and the concentration that synthetic rubber is soft section is: 2.0mol/L～27mol/L, and the monomer add-on of the hard section of synthetic plastics is 0.14mol/L～2.6mol/L; Initiator system (initiator and coinitiator) add-on is respectively: 1mol/L～10
-5Mol/L, 10mol/L～10
-4Mol/L is decided by the thermoplastic elastomer product performance; The nucleophilic reagent add-on is: 0.1mol/L～10
-6Mol/L is decided by the water content size and the initiator of system; The end-capping reagent add-on is: 1mol/L～10
-5Mol/L is decided by the initiator add-on; Terminator is 1L.
Temperature of reaction 0～-90 ℃, preferable temperature of reaction-70～-80 ℃.
The reaction times that synthetic rubber is soft period is 1 minute～3 hours, and the end-capping reagent ageing adds the monomer of the hard section of synthetic plastics after 10 minutes～2 hours then, continues reaction 1 minute～3 hours, adds terminator, precipitation, washing, drying.
Synthetic to dicumyl chlorine:
In the 250ml there-necked flask of funnel and reflux condensing tube is housed, add dicumyl alcohol, solvent C H
2Cl
2, be stirred to dicumyl alcohol is dissolved fully, under 0 ℃, in 30 minutes, drip SOCl
2, keep 0 ℃ and stir 3 hours after, reaction mixture 5%Na
2CO
3Solution washing three times is washed till neutrality with distilled water again, with anhydrous CaCl
2Dry more than 12 hours, to filter, filtrate is taken out CH
2Cl
2After, low temperature crystallization in normal hexane, products obtained therefrom fill nitrogen and preserve standby through the normal hexane recrystallization after the vacuum-drying.Reaction equation:
Density to dicumyl chlorine is 0.923 grams per milliliter for 20 ℃.
End-capping reagent 1 synthetic method:
In the there-necked flask that stirring and refluxing prolong and funnel are housed, add magnesium, bromobenzene successively, anhydrous diethyl ether, iodine, leave standstill, to the reaction initiation, adding bromobenzene and anhydrous diethyl ether then is the solution that is mixed with at 1: 4 with volume ratio, and the consumption of bromobenzene is 1.3 times of metered amount.Stirring reaction 30 minutes is got the methyl phenyl ketone of about 1.3 times of metered amounts and anhydrous diethyl ether with 1: 4 wiring solution-forming of volume ratio, splashes in the there-necked flask, about reaction half an hour.
NH 30%
4Cl solution adds in the above-mentioned system, separates organic phase.Water pump is taken out ether, adds normal hexane, is settled out the intermediate product methyl-diphenyl-carbinol, and is standby with normal hexane washing after drying.
The 100g methyl-diphenyl-carbinol adds 20% H
2SO
4Solution 250ml in there-necked flask, is heated to about 160 ℃ so that oil is molten, separates the water that produces, and the reaction times is 3～4 hours.Separate while hot, organic phase is dissolved with hexanaphthene, remove insolubles after, with anhydrous magnesium sulfate drying 24 hours, underpressure distillation went out product.Product is that orange has special odor, utmost point heavy-gravity liquid.
Reaction equation:
270 ℃ of 1 boiling points, 6 ℃ of fusing points, density is 1.0281 grams per milliliters for 20 ℃.
When synthesis technique of the present invention is applied for a patent, Shen Qing initiator system again, application number is: 98102282.0.
The drawing of accompanying drawing is described as follows:
Fig. 1 is synthesis technique figure of the present invention
The present invention will be described in further detail in conjunction with the embodiments:
Embodiment 1:
Polyindene-polyisobutene-polyindene inlay section thermal plastic elastic body
At normal pressure, temperature of reaction-75～-80 ℃ in the purified reaction vessel of drying, add the 1L mixed solvent, 3 * 10 under the exsiccant nitrogen protection
-3Mol/L is to dicumyl chlorine, 0.04mol/L TiCl
4, 1.8 * 10
-3The mol/L hexahydropyridine, ageing 15 minutes, adding make its concentration keep the 2.8mol/L iso-butylene, react after 1 hour, add the end-capping reagent 1, and concentration is 6 * 10
-3Mol/L, ageing 15 minutes adds plastic hard section monomer indenes, its concentration is 0.6mol/L, continues reaction 1 hour, adds the methyl alcohol that is dissolved with 5%HCl and stop in system, in a large amount of ethanolic soln of solution impouring after the termination, precipitation is separated out product, filters after drying.
Inlay section thermal plastic elastic body product number-average molecular weight 70500, molecular weight distribution are 1.32, and second-order transition temperature is 197 ℃, and tensile strength is 20MPa, and elongation is 400%, and shore hardness is 45.
Embodiment 2: synthetic polystyrene-polyisobutene-polystyrene block thermoplastic elastomer.
Synthesis technique is with embodiment 1, and difference is temperature of reaction-70～-75 ℃, TiCl
4Concentration be 6 * 10
-2Mol/L, the concentration of hexahydropyridine is 1.85 * 10
-3Mol/L, the concentration of end-capping reagent 1 is 4.5 * 10
-3Mol/L, the concentration of plastic hard section monomer styrene is 0.81mol/L, isobutylene concentration is 3.5 mol/L.
The number-average molecular weight of the hot elastomer product of block is 85700, and molecular weight distribution is 1.26, and tensile strength is 24MPa, and elongation is 750%.
Embodiment 3: synthetic poly alpha methylstyrene-polyisobutene-poly alpha methylstyrene inlay section thermal plastic elastic body.
Synthesis technique is with embodiment 1, and difference is temperature of reaction-70～-75 ℃, TiCl
4Concentration be 6 * 10
-2Mol/L, the concentration of hexahydropyridine is 1.85 * 10
-3Mol/L, end-capping reagent 1 are 4.5 * 10
-3Mol/L, plastic hard section monomer are alpha-methyl styrene, and its concentration is 0.63mol/L, and isobutylene concentration is 4.0mol/L.
Inlay section thermal plastic elastic body product number-average molecular weight is 94800, and molecular weight distribution is 1.44, and tensile strength is 25MPa, and elongation is 850%.
The present invention has following advantage compared to existing technology:
1. product molecular weight distribution is narrow, is generally between 1.2～1.5 block rate height, homopolymer content Low.
2. excellent product performance, its hot strength is 20～25MPa, percentage elongation is 400%～850%.
3. the present invention is directly for the elastomeric block copolymer of active cation method synthetic thermoplastic.
4. the present invention utilizes common chemical reagent molten for initator, coinitiator, nucleopilic reagent and mixing Agent is for the industrialization of this synthetic method provides advantage.
Claims (3)
1. the synthesis technique of the thermoplastic elastomer of active cation; this block polymer is connected the hard section of synthetic plastics by soft section of synthetic rubber and forms with its soft section two ends, it is characterized in that under normal pressure temperature of reaction 0～-90 ℃; under the exsiccant nitrogen protection, form by following several steps successively:
(1) mixed solvent; Initiator: a kind of compound or its mixture with following general formula
R wherein
1, R
2Represent hydrogen atom separately, R
1, R
2, R
3Represent C separately
1～C
8The straight or branched alkyl, R
2Represent five yuan, hexa-atomic saturated or unsaturated ring, R
1And R
2Form five yuan, hexa-atomic saturated or unsaturated ring, X representation hydroxy, ether, ester group, halogen with the carbon atom that links to each other together; The coinitiator Lewis acid; The nucleophilic reagent Lewis base, first ageing 10～60 minutes adds isobutylene monomer, makes soft section of active cation polyisobutylene synthetic rubber;
(2) thereafter, add end-capping reagent 1 or benzophenone, ageing 15 minutes adds the plastic hard section monomer;
(3) terminator is collected product from reaction mixture.
2. according to the synthesis technique of claim 1, it is characterized in that temperature of reaction-70～-80 ℃.
3. according to the synthesis technique of claim 1, it is characterized in that mixed solvent is the mixed solvent of methyl chloride and hexanaphthene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98102283A CN1062569C (en) | 1998-06-19 | 1998-06-19 | Synthesis technology for active cation thermoplastic elastic body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98102283A CN1062569C (en) | 1998-06-19 | 1998-06-19 | Synthesis technology for active cation thermoplastic elastic body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1204653A true CN1204653A (en) | 1999-01-13 |
| CN1062569C CN1062569C (en) | 2001-02-28 |
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ID=5217249
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98102283A Expired - Lifetime CN1062569C (en) | 1998-06-19 | 1998-06-19 | Synthesis technology for active cation thermoplastic elastic body |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1580090B (en) * | 2004-05-20 | 2010-12-29 | 北京石油化工学院 | Multi-arm star-type thermoplastic elastomer synthesizing method |
| CN102391444A (en) * | 2011-08-24 | 2012-03-28 | 苏州大学 | Amphipathic block copolymer containing polyisobutylene and polycation and preparation thereof |
| CN101987876B (en) * | 2009-08-03 | 2012-07-04 | 北京化工大学 | Controllable cation polymerizing method of vinyl monomers |
| CN103122052A (en) * | 2011-11-18 | 2013-05-29 | 北京化工大学 | Segmented copolymer with fully-saturated soft segment and crystallizable hard segment and preparation method of segmented copolymer |
| CN103897086A (en) * | 2014-03-05 | 2014-07-02 | 北京石油化工学院 | Preparation method of poly(isobutene-co-p-methylstyrene) random copolymer |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3946899A (en) * | 1975-02-07 | 1976-03-30 | Allain Charles V | Sugar cane planter |
| US5428111A (en) * | 1993-10-15 | 1995-06-27 | University Of Massachusetts | Living polymerization of olefins to produce copolymer |
-
1998
- 1998-06-19 CN CN98102283A patent/CN1062569C/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1580090B (en) * | 2004-05-20 | 2010-12-29 | 北京石油化工学院 | Multi-arm star-type thermoplastic elastomer synthesizing method |
| CN101987876B (en) * | 2009-08-03 | 2012-07-04 | 北京化工大学 | Controllable cation polymerizing method of vinyl monomers |
| CN102391444A (en) * | 2011-08-24 | 2012-03-28 | 苏州大学 | Amphipathic block copolymer containing polyisobutylene and polycation and preparation thereof |
| CN103122052A (en) * | 2011-11-18 | 2013-05-29 | 北京化工大学 | Segmented copolymer with fully-saturated soft segment and crystallizable hard segment and preparation method of segmented copolymer |
| CN103122052B (en) * | 2011-11-18 | 2015-12-09 | 北京化工大学 | A kind of soft section of crystallizable segmented copolymer of complete saturated hard section and preparation method thereof |
| CN103897086A (en) * | 2014-03-05 | 2014-07-02 | 北京石油化工学院 | Preparation method of poly(isobutene-co-p-methylstyrene) random copolymer |
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| Publication number | Publication date |
|---|---|
| CN1062569C (en) | 2001-02-28 |
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