CN109265897A - A kind of organic-silicon-modified polystyrene and preparation method thereof - Google Patents
A kind of organic-silicon-modified polystyrene and preparation method thereof Download PDFInfo
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- CN109265897A CN109265897A CN201811126901.XA CN201811126901A CN109265897A CN 109265897 A CN109265897 A CN 109265897A CN 201811126901 A CN201811126901 A CN 201811126901A CN 109265897 A CN109265897 A CN 109265897A
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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
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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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
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
- C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
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Abstract
The present invention relates to a kind of modified polymer materials more particularly to a kind of organic-silicon-modified polystyrene and preparation method thereof.The organic-silicon-modified polystyrene is prepared by both the component A containing organosilicon structures and the B component containing catalyst component compounding.Following four steps of preparation method: (1) prepared by component A；(2) preparation of B component；(3) it compounds；(4) it post-processes.The present invention overcomes polystyrene resin property in the prior art is more crisp, its shock resistance is poor, the bad problem of physics toughening effect, the invention has the following advantages: the polystyrene that (1) prepares through the invention has good toughness, good impact resistant effect；(2) present invention is chemical modification, more preferable compared to physical modification effect；(3) present invention also has good high temperature resistance.
Description
Technical field
The present invention relates to a kind of modified polymer material more particularly to a kind of organic-silicon-modified polystyrene and its preparation sides
Method.
Background technique
Polystyrene (Polystyrene, abridge PS) refers to by styrene monomer free radical addition polymerization poly-
Close object.It is a kind of colorless and transparent thermoplastic plastic, has the glass transition temperature higher than 100 DEG C, therefore be usually utilized to
Make disposable container of the various temperature for needing to bear boiled water, and disposable foam food boxes etc..
Polystyrene (PS) includes ordinary polystyrene, expanded polystyrene (EPS) (EPS), high impact polystyrene (HIPS) and
Syndiotactic polytyrene (SPS).Ordinary polystyrene resin is nontoxic, odorless, colourless transparent grain, like glassy brittleness material
Material, product have high transparency, and light transmittance is up to 90% or more, and electrical insulation capability is good, easy coloring, processing fluidity
It is good, rigidity is good and chemical corrosion resistance is good etc..Being disadvantageous in that property of ordinary polystyrene is crisp, and impact strength is low, easily occurs
Stress cracking, poor heat resistance and intolerant to boiling water etc..
Such as one kind a kind of disclosed ultra-toughness high impact polystyrene resin and its preparation work in Chinese patent literature
Skill is made by raw material blending extrusion, and makes to form physical crosslinking, according to parts by weight, major ingredient packet between the major ingredient in raw material
It includes: 70~90 parts of high impact polystyrene, 10~25 parts of thermoplastic elastomer (TPE).This ultra-toughness high impact polystyrene resin tool
There is the characteristics of light density is low, fatigue durability is good and good toughness, and poly- using the ultra-toughness high impact-resistant that the preparation process obtains
Styrene resin performance is stablized.But its toughening is to realize that, compared to chemical crosslinking, stability is poor by physical crosslinking,
Thus its toughening effect does not have chemical modification effective.
Summary of the invention
The present invention be in order to overcome in the prior art polystyrene resin property it is more crisp, shock resistance is poor, physics
The bad problem of toughening effect, the obvious problem of polystyrene resin brittleness can effectively be improved by providing one kind, keep it anti-
A kind of organic-silicon-modified polystyrene and preparation method thereof for non-physical toughening modifying that impact property significantly improves.
For achieving the above object, the invention is realized by the following technical scheme:
A kind of organic-silicon-modified polystyrene, the organic-silicon-modified polystyrene by the component A containing organosilicon structures with
And both B components containing catalyst component compounding is prepared.
Organic-silicon-modified polystyrene in the present invention by the component A containing organosilicon structures and contains catalyst component
Both B components compounding be prepared, organosilicon structures therein crosslink reaction under the effect of the catalyst, form it into
It is crosslinked inierpeneirating network structure, to effectively raise whole toughness and its impact resistance.Simultaneously as therein have
The addition of machine silicon structure, so that originally relatively stiff segment is become by the way that flexible preferable organosilicon structures flexibility is added
It is good.To improve its impact resistance from molecule angle.Meanwhile organosilicon structures have good high and low temperature resistance,
After organosilicon structures are added, the heat resistance of whole polystyrene has further promotion, while being crosslinked interpenetrating networks knot being formed
Its heat resistance is also obviously improved after structure.
Preferably, the organosilicon structures in the component A are methyl dimethoxy oxygroup silicon substrate, trimethoxy silicon substrate, two
Methoxyl group silicon substrate, phenyl dimethoxy silicon substrate, methyl diethoxy silicon substrate.
It all has methoxyl group or alkoxide for organosilicon structures in the present invention, under the effect of the catalyst,
Chemical crosslink reaction can effectively occur, to form crosslinking inierpeneirating network structure, improve its toughness.
Preferably, the quality of the organosilicon structures in the component A accounts for the 0.5~5% of component A total quality.
When the amount of organosilicon structures within this range when, main outstanding physical property will not change, still
There can be electrical insulation capability good, the advantages that easy coloring, processing fluidity is good, and rigidity is good and chemical corrosion resistance is good, but in fact
Impact resistance and heat resistance have further promotion.
Preferably, catalyst in the B component includes the first catalyst and the second catalyst, described first
Catalyst is dibutyl tin dilaurate, second catalyst be acetyl acetone salt, first catalyst with
The mass ratio of both second catalyst is (1~5): (1~3).
Catalyst in the present invention include dibutyl tin dilaurate its effectively the alkoxy on silicon atom can be existed
Water most with lower generation cross-linking reaction, to effectively form crosslinking inierpeneirating network structure.Meanwhile the second acetyl in catalyst
It can effectively participate in the cross-linking reaction in resin to acetone metal salt, with dibutyl tin dilaurate instrument concerted catalysis, reach
To best catalytic condition.
Preferably, the acetyl acetone salt is chromium acetylacetonate, ferric acetyl acetonade, acetylacetone cobalt, acetyl
One of acetone zirconium, vanadium acetylacetonate, titanium acetylacetone, aluminium acetylacetonate or zinc acetylacetonate.
Preferably, the catalyst content in the B component accounts for the 0.001~0.05% of B component total quality.
Preferably, in the organic-silicon-modified polystyrene mass ratio of component A and B component be 100:(25~
40)。
A kind of preparation method of foregoing organic-silicon-modified polystyrene, the preparation method following steps:
(1) prepared by component A: the catalysis by polystyrene master batch with the silane containing vinyl structure in cumyl peroxide issues
Raw graft reaction, obtains the component A containing organosilicon structures；
(2) polystyrene master batch and catalyst the preparation of B component: are obtained into the B component containing catalyst component after evenly mixing；
(3) compound: extruding pelletization after component A is blended with B component obtains organic-silicon-modified polystyrene master batch；
(4) it post-processes: organic-silicon-modified polystyrene master batch being placed in saturated vapor after curing and obtain organic-silicon-modified polyphenyl
Ethylene.
The present invention is finally granulated by the mutual compounding between component A and B component and obtains machine Si modification polystyrene mother
Grain, and the alkoxy silane for acting on being participated in organosilicon structures by the steam in saturated vapor post-processed is being catalyzed
Cross-linking reaction under agent effect forms crosslinking inierpeneirating network structure
Preferably, the mass ratio in the step (1) between cumyl peroxide and polystyrene master batch is 0.5~1:
100, the graft reaction temperature is 125~150 DEG C.
Preferably, the temperature of saturated vapor is 110~125 DEG C in the step (4), steam pressure 0.5~
1.2bar, curing time are 0.5~5 hour.
Therefore, the invention has the following advantages:
(1) polystyrene prepared through the invention has good toughness, good impact resistant effect；
(2) present invention is chemical modification, more preferable compared to physical modification effect；
(3) present invention also has good high temperature resistance.
Specific embodiment
Technical solution of the present invention is made to further describe explanation below by specific embodiment.
If saying that the raw material of use is raw material commonly used in the art without specified otherwise, in the embodiment of the present invention, implement
Method employed in example, is the conventional method of this field.
Embodiment 1
A kind of organic-silicon-modified polystyrene, the organic-silicon-modified polystyrene is by containing methyl dimethoxy oxygroup silicon substrate
Both the component A of structure and the B component containing catalyst component, which compound, to be prepared, and the mass ratio of component A and B component is
100:25, wherein the quality of the organosilicon structures in the component A accounts for the 0.5% of component A total quality, the B component
In catalyst include the first catalyst and the second catalyst, first catalyst be dibutyl tin dilaurate, institute
The second catalyst stated is chromium acetylacetonate, and the mass ratio of first catalyst and both the second catalyst is 1:1, described
B component in catalyst content account for the 0.001% of B component total quality.
The preparation method of the organic-silicon-modified polystyrene before a kind of, the preparation method following steps:
(1) prepared by component A: by polystyrene master batch and methylvinyldimethoxysilane cumyl peroxide catalysis
Lower generation graft reaction, obtains the component A containing organosilicon structures, and the methylvinyldimethoxysilane quality accounts for A
The 0.5% of component total quality, the mass ratio between the cumyl peroxide and polystyrene master batch are 0.5:100,
The graft reaction temperature is 125 DEG C；
(2) polystyrene master batch and catalyst the preparation of B component: are obtained into the B component containing catalyst component after evenly mixing；
(3) compound: extruding pelletization after component A is blended with B component according to mass ratio 100:25 obtains organic-silicon-modified polyphenyl second
Alkene master batch；
(4) post-process: it is 110 DEG C that organic-silicon-modified polystyrene master batch, which is placed in temperature, and the saturation of steam pressure 0.5bar is steamed
Organic-silicon-modified polystyrene is obtained after curing 0.5 hour in vapour.
Embodiment 2
A kind of organic-silicon-modified polystyrene, the organic-silicon-modified polystyrene is by containing trimethoxy silicon substrate structure
Component A and both B components containing catalyst component compounding be prepared, the mass ratio of component A and B component is 100:
40, wherein the quality of the organosilicon structures in the component A accounts for the 5% of component A total quality, urging in the B component
Agent includes the first catalyst and the second catalyst, and first catalyst is dibutyl tin dilaurate, and described the
Two catalyst are ferric acetyl acetonade, and the mass ratio of first catalyst and both the second catalyst is 5:3, the B group
Catalyst content in point accounts for the 0.05% of B component total quality.
The preparation method of the organic-silicon-modified polystyrene before a kind of, the preparation method following steps:
(1) prepared by component A: polystyrene master batch and vinyltrimethoxysilane are issued in the catalysis of cumyl peroxide
Raw graft reaction, obtains the component A containing organosilicon structures, and the vinyltrimethoxysilane quality accounts for component A entirety
The 5% of quality, the mass ratio between the cumyl peroxide and polystyrene master batch is 1:100, and the grafting is anti-
Answering temperature is 150 DEG C；
(2) polystyrene master batch and catalyst the preparation of B component: are obtained into the B component containing catalyst component after evenly mixing；
(3) compound: extruding pelletization after component A is blended with B component according to mass ratio 100:40 obtains organic-silicon-modified polyphenyl second
Alkene master batch；
(4) post-process: it is 125 DEG C that organic-silicon-modified polystyrene master batch, which is placed in temperature, and the saturation of steam pressure 1.2bar is steamed
Organic-silicon-modified polystyrene is obtained after curing 5 hours in vapour.
Embodiment 3
A kind of organic-silicon-modified polystyrene, the organic-silicon-modified polystyrene is by containing dimethoxy silicon substrate structure
Component A and both B components containing catalyst component compounding be prepared, the mass ratio of component A and B component is 100:
35, wherein the quality of the organosilicon structures in the component A accounts for the 2.5% of component A total quality, in the B component
Catalyst includes the first catalyst and the second catalyst, and first catalyst is dibutyl tin dilaurate, described
Second catalyst is acetylacetone cobalt, and the mass ratio of first catalyst and both the second catalyst is 2:2, the B
Catalyst content in component accounts for the 0.025% of B component total quality.
The preparation method of the organic-silicon-modified polystyrene before a kind of, the preparation method following steps:
(1) prepared by component A: polystyrene master batch and vinyl dimethoxysilane are issued in the catalysis of cumyl peroxide
Raw graft reaction, obtains the component A containing organosilicon structures, and the vinyl dimethoxysilane quality accounts for component A entirety
The 2.5% of quality, the mass ratio between the cumyl peroxide and polystyrene master batch is 0.8:100, and described connects
Branch reaction temperature is 140 DEG C；
(2) polystyrene master batch and catalyst the preparation of B component: are obtained into the B component containing catalyst component after evenly mixing；
(3) compound: extruding pelletization after component A is blended with B component according to mass ratio 100:35 obtains organic-silicon-modified polyphenyl second
Alkene master batch；
(4) post-process: it is 115 DEG C that organic-silicon-modified polystyrene master batch, which is placed in temperature, the saturated vapor of steam pressure 1bar
Middle curing obtained organic-silicon-modified polystyrene after 2 hours.
Embodiment 4
A kind of organic-silicon-modified polystyrene, the organic-silicon-modified polystyrene is by containing phenyl dimethoxy silicon substrate
Both the component A of structure and the B component containing catalyst component, which compound, to be prepared, and the mass ratio of component A and B component is
100:30, wherein the quality of the phenyl dimethoxy silicon substrate structure in the component A accounts for the 1.5% of component A total quality,
Catalyst in the B component includes the first catalyst and the second catalyst, and first catalyst is tin dilaurate
Dibutyl tin, second catalyst are titanium acetylacetone, the quality of first catalyst and both the second catalyst
Than for 4:1, the catalyst content in the B component accounts for the 0.035% of B component total quality.
The preparation method of the organic-silicon-modified polystyrene before a kind of, the preparation method following steps:
(1) prepared by component A: by polystyrene master batch and ethenylphenyl dimethoxysilane cumyl peroxide catalysis
Lower generation graft reaction, obtains the component A containing organosilicon structures, and the ethenylphenyl dimethoxysilane quality accounts for A
The 1.5% of component total quality, the mass ratio between the cumyl peroxide and polystyrene master batch are 0.9:100,
The graft reaction temperature is 145 DEG C；
(2) polystyrene master batch and catalyst the preparation of B component: are obtained into the B component containing catalyst component after evenly mixing；
(3) compound: extruding pelletization after component A is blended with B component according to mass ratio 100:30 obtains organic-silicon-modified polyphenyl second
Alkene master batch；
(4) post-process: it is 120 DEG C that organic-silicon-modified polystyrene master batch, which is placed in temperature, and the saturation of steam pressure 1.1bar is steamed
Organic-silicon-modified polystyrene is obtained after curing 4.5 hours in vapour.
Embodiment 5
A kind of organic-silicon-modified polystyrene, the organic-silicon-modified polystyrene is by containing methyl diethoxy silicon substrate
Both the component A of structure and the B component containing catalyst component, which compound, to be prepared, and the mass ratio of component A and B component is
100:35, wherein the quality of the methyl diethoxy silicon substrate structure in the component A accounts for the 4.5% of component A total quality,
Catalyst in the B component includes the first catalyst and the second catalyst, and first catalyst is tin dilaurate
Dibutyl tin, second catalyst are aluminium acetylacetonate, the quality of first catalyst and both the second catalyst
Than for 5:2, the catalyst content in the B component accounts for the 0.045% of B component total quality.
The preparation method of the organic-silicon-modified polystyrene before a kind of, the preparation method following steps:
(1) prepared by component A: by polystyrene master batch and methyl vinyl diethoxysilane cumyl peroxide catalysis
Lower generation graft reaction, obtains the component A containing organosilicon structures, and the methyl vinyl diethoxysilane quality accounts for A
The 3.5% of component total quality, the mass ratio between the cumyl peroxide and polystyrene master batch are 0.6:100,
The graft reaction temperature is 135 DEG C；
(2) polystyrene master batch and catalyst the preparation of B component: are obtained into the B component containing catalyst component after evenly mixing；
(3) compound: extruding pelletization after component A is blended with B component obtains organic-silicon-modified polystyrene master batch；
(4) post-process: it is 120 DEG C that organic-silicon-modified polystyrene master batch, which is placed in temperature, and the saturation of steam pressure 0.9bar is steamed
Organic-silicon-modified polystyrene is obtained after curing 3.5 hours in vapour.
Organic-silicon-modified polystyrene that Examples 1 to 5 obtains and commercially available polystyrene are tested, wherein stretching
Intensity is measured according to GB/T1040.2-2006 " plastic tensile method for testing performance "；Izod notch impact strength is according to GB/
T1843-2008 " measurement of plastics cantilever beam impact strength " is measured；Fatigue durability: by doubling 125*10*3.2mm and
The finished product of 125*10*1.6mm, continuous doubling 60 times unbroken, then judges that fatigue performance is excellent, does not break for continuous doubling 40-60 times
It splits, then judges that fatigue performance is good；Continuous doubling is broken less than 40 times, then fatigue performance is poor.
The test result of 1 Examples 1 to 5 of table and commercially available comparative example
Organic-silicon-modified polystyrene obtained is not under the premise of influencing to draw high intensity through the invention known to from upper table, energy
Enough effective impact strengths for promoting polystyrene, to prove effectively improve the tough of polystyrene plastics through the invention
Property.
Claims (10)
1. a kind of organic-silicon-modified polystyrene, which is characterized in that the organic-silicon-modified polystyrene is by containing organosilicon
Both the component A of structure and the B component containing catalyst component, which compound, to be prepared.
2. a kind of organic-silicon-modified polystyrene according to claim 1, which is characterized in that having in the component A
Machine silicon structure is methyl dimethoxy oxygroup silicon substrate, trimethoxy silicon substrate, dimethoxy silicon substrate, phenyl dimethoxy silicon substrate, methyl two
Ethyl-silicone.
3. a kind of organic-silicon-modified polystyrene according to claim 1 or 2, which is characterized in that in the component A
The quality of organosilicon structures accounts for the 0.5 ~ 5% of component A total quality.
4. a kind of organic-silicon-modified polystyrene according to claim 1, which is characterized in that urging in the B component
Agent includes the first catalyst and the second catalyst, and first catalyst is dibutyl tin dilaurate, and described the
Two catalyst are acetyl acetone salt, and the mass ratio of first catalyst and both the second catalyst is (1 ~ 5): (1 ~
3).
5. a kind of organic-silicon-modified polystyrene according to claim 4, which is characterized in that the cetylacetone metallic
Salt is chromium acetylacetonate, ferric acetyl acetonade, acetylacetone cobalt, acetylacetone,2,4-pentanedione zirconium, vanadium acetylacetonate, titanium acetylacetone, levulinic
One of ketone aluminium or zinc acetylacetonate.
6. a kind of organic-silicon-modified polystyrene according to claim 1 or 4, which is characterized in that in the B component
Catalyst content accounts for the 0.001 ~ 0.05% of B component total quality.
7. a kind of organic-silicon-modified polystyrene according to claim 1, which is characterized in that described is organic-silicon-modified poly-
The mass ratio of component A and B component is 100:(25 ~ 40 in styrene).
8. a kind of preparation method of the organic-silicon-modified polystyrene as described in any one of claim 1 ~ 7, feature exist
In the preparation method following steps:
(1) prepared by component A: the catalysis by polystyrene master batch with the silane containing vinyl structure in cumyl peroxide issues
Raw graft reaction, obtains the component A containing organosilicon structures；
(2) polystyrene master batch and catalyst the preparation of B component: are obtained into the B component containing catalyst component after evenly mixing；
(3) compound: extruding pelletization after component A is blended with B component obtains organic-silicon-modified polystyrene master batch；
(4) it post-processes: organic-silicon-modified polystyrene master batch being placed in saturated vapor after curing and obtain organic-silicon-modified polyphenyl
Ethylene.
9. a kind of preparation method of organic-silicon-modified polystyrene according to claim 8, which is characterized in that the step
Suddenly the mass ratio in (1) between cumyl peroxide and polystyrene master batch is 0.5 ~ 1:100, the graft reaction temperature
It is 125 ~ 150 DEG C.
10. a kind of preparation method of organic-silicon-modified polystyrene according to claim 8, which is characterized in that described
The temperature of saturated vapor is 110 ~ 125 DEG C, 0.5 ~ 1.2bar of steam pressure in step (4), and the curing time is 0.5 ~ 5 hour.
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Citations (3)
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|---|---|---|---|---|
| US4528301A (en) * | 1983-06-23 | 1985-07-09 | Gbf, Inc. | Oxygen permeable, styrene based, contact lens material |
| CN106751095A (en) * | 2016-12-26 | 2017-05-31 | 沈阳化工大学 | Isomerism containing L POSS crosslinking agents is modified to reclaim PS and preparation method thereof |
| CN107108771A (en) * | 2014-12-12 | 2017-08-29 | 东亚合成株式会社 | Two-liquid type solidification compound |
-
2018
- 2018-09-26 CN CN201811126901.XA patent/CN109265897A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4528301A (en) * | 1983-06-23 | 1985-07-09 | Gbf, Inc. | Oxygen permeable, styrene based, contact lens material |
| CN107108771A (en) * | 2014-12-12 | 2017-08-29 | 东亚合成株式会社 | Two-liquid type solidification compound |
| CN106751095A (en) * | 2016-12-26 | 2017-05-31 | 沈阳化工大学 | Isomerism containing L POSS crosslinking agents is modified to reclaim PS and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 何红运等: "《综合化学实验（一）》", 31 October 2015, 湖南师范大学出版社 * |
| 冯春详等: "《元素有机化合物及其聚合物》", 31 March 1999, 国防科技大学出版社 * |
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