CN106554474B - It is a kind of low from method of the membrane swelling rate linear hydrogenated styrene analog thermoplastic elastomer from membrane swelling - Google Patents
It is a kind of low from method of the membrane swelling rate linear hydrogenated styrene analog thermoplastic elastomer from membrane swelling Download PDFInfo
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Abstract
The invention discloses a kind of low die swell ratio linear hydrogenated process for preparing thermoplastic phenylethylene elastomer; this method is under inert gas protection; using alkanes as solvent; using styrene monomer and conjugate diene monomer; in the presence of alkyl lithium initiator and polar structure are adjusted; anionic polymerisation is carried out, polymerizate passes through titanocenes catalyst to catalyzing hydrogenating, obtains linear hydrogenated styrene analog thermoplastic elastomer；Anionic polymerisation carries out one-step polymerization the following steps are included: styrene monomer is added in (1)；(2) styrene monomer and butadiene and/or isoprene monomer is added simultaneously, or the two sections of polymerizations of divinylic monomer and isoprene monomer progress is added simultaneously, (3) are added styrene monomer and carry out three stage polymerization；The linear hydrogenated styrenic thermoplastic elastomer's die swell ratio obtained with this method is below 20%.
Description
Technical field
The present invention relates to a kind of preparation sides of linear hydrogenated styrene analog thermoplastic elastomer with low from membrane swelling rate
Method, and in particular to improve selective hydration, control distribution styrene-butadiene/styrene-styrene (hSBSS, also by
The referred to as benzene second of the hydrogenation of styrene-ethylene Butadiene/Styrene-styrene (S-EB/S-S) block copolymer and selectivity
Alkene-butadiene/isoprene styrene (hSIBS, also referred to as styrene-ethylene butadiene/isoprene styrene (S-
EB/P-S) method of the block copolymer from membrane swelling.
Background technique
It is related to macromolecule melt elastic memory capacity from membrane swelling.Melt is when entering mouth mold, by strong stretching
And shearing deformation, wherein tensile deformation category elastic deformation.These deformation are only partially relaxed in mouth mold, and remainder exists
Elastic recovery occurs after extrusion neck ring mold, extrusion swelling phenomenon occurs.When extrusion temperature raising or extruded velocity decline or system
Middle addition filler and cause macromolecule melt elastic deformation reduce when, extrusion swelling phenomenon is substantially reduced.
In general, the activity of strand or segment reduces, the active force between macromolecular is reduced, and elasticity reduces, swollen
Swollen rate reduces.Linear hydrogenated styrenic thermoplastic elastomer uses using three steps hair method through anionic solution polymerization, and one section one
As polymerize for styrene or α-methylstyrene, two sections of butadiene or isoprene polymerization, three sections are styrene or Alpha-Methyl benzene
Vinyl polymerization, then carry out the synthesizing hydrogenated styrenic elastomer of agent hydrogenation.The linear hydrogenated styrenic thermoplastic synthesized
Elastic molecule segment is regular, and the active force between molecule is big, and elasticity is high, and expansion rate is big.
In the prior art as Chinese patent (publication number CN102875889) discloses a kind of raising stability of polypropylene melt
Method, the patent be by and meanwhile add tetrafluoro ethylene polymer with reinforced polypropylene melt strength function and have and control
The sheet component physical blending of melt die swelling function processed achievees the purpose that reduce melt die swelling phenomenon, but does not refer to conjunction
Improvement at process to melt stability；Chinese patent (publication number CN85102259) discloses the preparation of block copolymer, should
Patent is about the technology for reducing block copolymer SDS set deformation volume, i.e., during one-step polymerization plus such as a small amount of conjugation two
Alkene is into styrene monomer, but this method dosage is difficult to realize industrialized production less；Chinese patent (discloses
CN1376721A a kind of method for reducing permanent deformation of low-learity styrene type thermoplastic elastomer) is disclosed, this method mainly relates to
And type SBS, SIS, m-SBM-S, to the styrene monomer of hydrogenation without reference to；Although Chinese patent (publication number
CN85102259) and Chinese patent (disclosing CN1376721A) may be implemented permanent deformation 44% hereinafter, but there is no with
For the purpose of control die swelling.
Summary of the invention
Have the defects that, this hair high from membrane swelling rate for linear hydrogenated styrene analog thermoplastic elastomer in the prior art
Bright purpose is to be to provide a kind of preparation of linear hydrogenated styrene analog thermoplastic elastomer of the die swell ratio lower than 20%
Method, this method is easy to operate, is able to achieve using existing process equipment, cost is relatively low, meets demand of industrial production.
In order to realize technical purpose of the invention, the present invention provides a kind of low die swell ratio linear hydrogenated phenylethylenes
Process for preparation of thermoplastic elastomer, under inert gas protection, using alkanes as solvent, using styrene monomer and conjugation
Diene monomers carry out anionic polymerisation in the presence of alkyl lithium initiator and polar structure are adjusted, and polymerizate passes through two
Metallocene-titanium catalyst catalytic hydrogenation obtains linear hydrogenated styrene analog thermoplastic elastomer；The anionic polymerisation includes
Following steps: (1) it is added styrene monomer and carries out one-step polymerization；(2) be added simultaneously styrene monomer and butadiene and/or
Isoprene monomer, or divinylic monomer and isoprene monomer are added simultaneously and carries out two sections of polymerizations, initiation temperature is 50~
60 DEG C, reaction maximum temperature must not exceed 100 DEG C；(3) styrene monomer is added and carries out three stage polymerization；The anion is poly-
Close the gross mass of styrene monomer and the mass percent of butadiene and/or isoprene monomer in reaction process be 13~
45%:87~55%.
In technical solution of the present invention, by a certain proportion of styrene monomer and conjugated diene monomer or conjugation two
Alkene mix monomer is added in reaction system simultaneously, at moderate temperatures initiated polymerization, passes through strict control raw material monomer ratio
The conditions such as example, reaction temperature guarantee to generate one in polymerized conjugated diene soft segment to regulate and control the reactivity ratio of monomer in the course of the polymerization process
Segment random copolymer increases branch point, and does not influence the two-phase laminated flow effect of entire polymerizate.Pass through entire polymer
Have after hydrogenation low from membrane swelling rate.
In preferred scheme, in two sections of polymerization processes, using styrene monomer and butadiene and/or isoprene monomer
When, the mass percentage content of styrene is 5~23%；When using divinylic monomer and isoprene monomer, isoprene
Mass percentage content is 2~25%.
In preferred scheme, in one-step polymerization reaction process, initiation temperature is 45~55 DEG C, and reaction maximum temperature is no more than
75℃。
More preferably in scheme, the one-step polymerization time is 20~50min.
In preferred scheme, two sections of polymerization times are 20~50min.
In preferred scheme, in three stage polymerization reaction process, initiation temperature is 50~60 DEG C, and reaction maximum temperature is no more than
100℃；
More preferably in scheme, the three stage polymerization time is 20~50min.
In preferred scheme, hydrogenation time is 60~120min.
In preferred scheme, the mass percent of total monomer raw material is dense in alkane solvents during anionic polymerisation
Degree is 8~20%.
In preferred scheme, the polar structure regulator is tetrahydrofuran, ether, ethyl methyl ether, methyl phenyl ethers anisole, hexichol
Ether, glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofurfuryl alcohol ethylether, triethylamine, 6-methyl phosphonic triamide, tetramethyl second
At least one of diamines, double tetrahydro chaff propane and N, N- dimethyl tetrahydro chaff amine；Most preferred polar structure regulator is double
Tetrahydro chaff propane.
In preferred scheme, content of the polar structure regulator in alkane solvents is 5~210mg/kg.
In preferred scheme, the number-average molecular weight of linear hydrogenated styrene analog thermoplastic elastomer is 45000~160000,
Molecular weight distributing index≤1.07.
In preferred scheme, styrene monomer is styrene and/or α-methylstyrene.
In preferred scheme, using n-BuLi or s-butyl lithium as initiator.
In preferred scheme, hexamethylene or hexamethylene ethane mixed liquor etc. are solvent, and appropriate regulator is added.
The present invention provides a kind of technical indicator measured polymer and be appropriate for extrusioning blowing process, makes melt swollen from mould
Swollen variability (MOR).MOR can be measured by the Melt Flow Rate Measurer of standard, the method is as follows:
At a constant temperature, it is combined by different counterweights to adjust extrusion pressure, to obtain different extruded velocities.Root
According to the difference of melt flow rate (MFR) (MFR), usually extruded velocity is controlled in 15cm/100s, 15cm/200s or 15cm/
300s, MFR smaller can choose slower extruded velocity.Under constant extruded velocity, length squeezing greater than 15cm is obtained
Batten out, picture takes 15cm ± 1mm since initial extruding end, and with the average diameter Dmax at vernier caliper measurement both ends, MOR is under
Formula is calculated:
MOR=(Dmax-DMark)/DMark× 100%
DMark- indicate port mould diameter.
The factor for influencing MOR test result is temperature and extruded velocity, therefore, under stationary temperature and extruded velocity,
The MOR of same polymer is comparable, and can be used for quality control.Under identical extruded velocity, different types of polymers
MOR also has referring to meaning.The test result that vacant level HDPE is obtained referring in, product require polymer MOR less than 20%.
The hydrogenation line style styrene analog thermoplastic elastomer obtained using the present invention, (200 DEG C, 15cm/100s) of MOR logical
Often less than 20%, more preferably the result is that less than 10%, it can be ensured that melt sizes are stablized, and have the advantages that processing is stable.
Compared with the prior art, technical solution of the present invention has the advantage that
1, the linear hydrogenated styrene analog thermoplastic elastomer die swell ratio prepared is smaller, below 20%.
2, linear hydrogenated process for preparing thermoplastic phenylethylene elastomer is easy to operate, industrialized production easy to accomplish.
Detailed description of the invention
[Fig. 1] is the nucleus magnetic hydrogen spectrum figure of hydrogenated styrene thermoplastic elastomer prepared by the embodiment of the present invention 1.
Specific embodiment
Following embodiment and result can help to illustrate the principle of the present invention and basic skills, but the present patent application protection
Interest field is not limited to that.
Embodiment 1
In processing completely and the hexamethylene (water measured is added in 5 liters of polymeric kettles of high pure nitrogen displacement (band stirring)
Value < 20ppm), styrene, regulator, kettle is warming up to 45~55 DEG C, is added initiator n-BuLi (or s-butyl lithium), instead
30min is answered, by the styrene measured, butadiene while being added in reaction kettle, control maximum temperature must not exceed 100 DEG C, instead
30min is answered, styrene is eventually adding, reacts 30min.Glue is introduced into 5 liters plus hydrogen kettle after the completion of polymerization reaction, is warming up to 70
DEG C, hydrogenation catalyst is added, hydrogenation pressure is 0.8~1.5Mpa, hydrogenation reaction 120min.After hydrogenation reaction, terminate anti-
It answers, purify glue, discharge, antioxidant is added, glue obtains white polymer through cohesion, both obtains product after drying.With benzene second
Alkene, butadiene are that reaction monomers carry out different styrene and butadiene proportioning test, experimental data are listed in table 1.
Table 1
Embodiment 2
It substitutes two sections of styrene with isoprene to be tested, for reaction condition with example 1, experimental data is listed in table 2.
Table 2
Comparison example 1
Two sections of all butadiene compare test, and for reaction condition with example 1, experimental data is listed in table 3.
Table 3
Claims (13)
1. a kind of low die swell ratio linear hydrogenated process for preparing thermoplastic phenylethylene elastomer, in inert gas shielding
Under, using alkanes as solvent, using styrene monomer and conjugate diene monomer, adjusted in alkyl lithium initiator and polar structure
In the presence of agent, anionic polymerisation is carried out, polymerizate passes through titanocenes catalyst to catalyzing hydrogenating, obtains linear hydrogenated benzene second
Ethylenic thermoplastic elastomer；It is characterized in that, the anionic polymerisation is the following steps are included: phenylethylene is added in (1)
Monomer carries out one-step polymerization；(2) divinylic monomer is added simultaneously and isoprene monomer carries out two sections of polymerizations, initiation temperature 50
~60 DEG C, reaction maximum temperature must not exceed 100 DEG C；(3) styrene monomer is added and carries out three stage polymerization；The anion
In polymerization process the mass percent of the gross mass of styrene monomer and butadiene and isoprene monomer be 13~
45%:87~55%；In two sections of polymerization processes, when using divinylic monomer and isoprene monomer, the quality hundred of isoprene
Dividing than content is 2~25%.
2. low die swell ratio linear hydrogenated process for preparing thermoplastic phenylethylene elastomer according to claim 1,
It is characterized in that, initiation temperature is 45~55 DEG C in one-step polymerization reaction process, reaction maximum temperature is no more than 75 DEG C.
3. low die swell ratio linear hydrogenated process for preparing thermoplastic phenylethylene elastomer according to claim 2,
It is characterized in that, the one-step polymerization time is 20~50min.
4. low die swell ratio linear hydrogenated process for preparing thermoplastic phenylethylene elastomer according to claim 1,
It is characterized in that, two sections of polymerization times are 20~50min.
5. low die swell ratio linear hydrogenated process for preparing thermoplastic phenylethylene elastomer according to claim 1,
It is characterized in that, initiation temperature is 50~60 DEG C in three stage polymerization reaction process, reaction maximum temperature is no more than 100 DEG C；
6. low die swell ratio linear hydrogenated process for preparing thermoplastic phenylethylene elastomer according to claim 5,
It is characterized in that, the three stage polymerization time is 20~50min.
7. low die swell ratio linear hydrogenated process for preparing thermoplastic phenylethylene elastomer according to claim 1,
It is characterized in that, hydrogenation time is 60~120min.
8. low die swell ratio linear hydrogenated process for preparing thermoplastic phenylethylene elastomer according to claim 1,
The mass percent concentration of total monomer raw material is 8~20% in alkane solvents during anionic polymerisation.
9. low die swell ratio linear hydrogenated process for preparing thermoplastic phenylethylene elastomer according to claim 1,
It is characterized in that, the polar structure regulator is tetrahydrofuran, ether, ethyl methyl ether, methyl phenyl ethers anisole, diphenyl ether, ethylene glycol
Dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofurfuryl alcohol ethylether, triethylamine, 6-methyl phosphonic triamide, tetramethylethylenediamine, double four
Hydrogen chaff propane and N, at least one of N- dimethyl tetrahydro chaff amine.
10. low die swell ratio linear hydrogenated process for preparing thermoplastic phenylethylene elastomer according to claim 9,
It is characterized in that, the polar structure regulator is double tetrahydro chaff propane.
11. the according to claim 1, system of low die swell ratio linear hydrogenated styrene analog thermoplastic elastomer described in 9 or 10
Preparation Method, which is characterized in that content of the polar structure regulator in alkane solvents is 5~210mg/kg.
12. low die swell ratio linear hydrogenated process for preparing thermoplastic phenylethylene elastomer according to claim 1,
It is characterized in that, the number-average molecular weight of linear hydrogenated styrene analog thermoplastic elastomer is 45000~160000, molecular weight distribution
Index≤1.07.
13. low die swell ratio linear hydrogenated process for preparing thermoplastic phenylethylene elastomer according to claim 1,
It is characterized in that, the styrene monomer is styrene and/or α-methylstyrene.
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| CN1182169C (en) * | 2002-03-30 | 2004-12-29 | 中国石化集团巴陵石油化工有限责任公司 | Process for reducing permanent deformation of low-learity styrene type thermoplastic elastomer |
| JP4572058B2 (en) * | 2003-03-10 | 2010-10-27 | 電気化学工業株式会社 | Block copolymer and heat shrinkable film thereof |
| CN100341910C (en) * | 2004-01-17 | 2007-10-10 | 中国石化北京燕化石油化工股份有限公司 | Phenylethylene-isoprene/butadiene-phenylethylene ternary block copolymer and its preparation method |
| CN100369941C (en) * | 2005-05-17 | 2008-02-20 | 北京化工大学 | Hydrogenated styrene analog thermoplastic elastomer and its preparation method |
| JP5481131B2 (en) * | 2009-08-31 | 2014-04-23 | 電気化学工業株式会社 | Vinyl aromatic hydrocarbon resin composition suitable for blow molding |
| CN104312076A (en) * | 2014-10-13 | 2015-01-28 | 宁波景逸塑胶有限公司 | Thermoplastic styrene-butadiene rubber used in medical treatment field and preparation method of thermoplastic styrene-butadiene rubber |
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