CN106751095B - Isomerism containing L-POSS crosslinking agents is modified recycling PS and preparation method thereof - Google Patents
Isomerism containing L-POSS crosslinking agents is modified recycling PS and preparation method thereof Download PDFInfo
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- CN106751095B CN106751095B CN201611215789.8A CN201611215789A CN106751095B CN 106751095 B CN106751095 B CN 106751095B CN 201611215789 A CN201611215789 A CN 201611215789A CN 106751095 B CN106751095 B CN 106751095B
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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
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/20—Recycled plastic
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Abstract
Isomerism containing L-POSS crosslinking agents is modified recycling PS and preparation method thereof, is related to a kind of recycling PS and preparation method thereof, recycling PS is dried；By micro- crosslinking masterbatch made from the melting mixings extruding pelletization such as L-POSS crosslinking agents and dried recycling PS, initiator, catalyst, antioxidant, production aqua, it is first put into Universalpulverizer and places into planetary ball mill and grind, then high-speed mixer and mixing is put into dried recycling PS, micro- crosslinking masterbatch, toughener and inorganic filler by weight ratio, finally with extruding pelletization under double screw extruder up to modification regeneration PS.Since this crosslinking agent contains L-POSS and silane composition simultaneously, therefore this is that one kind having both the two performance, the novel crosslinker simultaneously with high temperature resistant and cross-linking properties can also improve its tensile strength while can improving recycling PS impact strengths, improve the mechanical property of PS.
Description
Technical field
The present invention relates to a kind of recycling PS and preparation method thereof, more particularly to a kind of homogeneity containing L-POSS crosslinking agents
Isomery is modified recycling PS and preparation method thereof.
Background technology
Polystyrene（PS）It is polymer free radical addition polymerization by styrene monomer.PS is a kind of with excellent
The features such as different electrical property, thermal stability and mobility, therefore disposable tableware, the vapour being usually utilized in manufacture daily life
Vehicle component, packaging material, toy, construction material, electric appliance and household supplies etc..But without modified PS resin elasticities modulus,
The shortcomings that poor mechanical properties such as tensile strength and impact strength, elongation at break is larger, poor heat resistance, these disadvantages limit it
Application in many fields.Therefore need to find the cross-linking reaction that a kind of high temperature resistant crosslinking agent is used to recycle PS, to reach
Isomerism cross-linking method activeness and quietness recycles the purpose of PS.
L-POSS is a kind of siloxanes with trapezium structure, in molecular structure containing the larger Si-O keys of bond energy and
Si-C is keyed the trapezium structure to be formed, be it is a kind of with Si-O for inorganic kernel, larger trapezoidal netted point of intermolecular force
Minor structure, this molecular structure have good high temperature resistant and mechanical property, and the Si-H in molecular structure can be with vinyl
Vinyl in silane crosslinker, which combines, forms the silane crosslinker containing L-POSS, since this crosslinking agent contains L-POSS simultaneously
With silane composition, therefore this is that one kind both having both performance, i.e., has the novel crosslinker of high temperature resistant and cross-linking properties simultaneously.
Invention content
The purpose of the present invention is to provide a kind of, and the isomerism containing L-POSS crosslinking agents is modified recycling PS and its preparation
Method, synthetic cross-linking agent of the present invention contains L-POSS and silane composition simultaneously, therefore this is that one kind having both the two performance, i.e., simultaneously
Novel crosslinker with high temperature resistant and cross-linking properties can also improve its stretching while can improving recycling PS impact strengths
Intensity improves the mechanical property of PS.
The purpose of the present invention is what is be achieved through the following technical solutions：
A kind of isomerism modification recycling PS containing L-POSS crosslinking agents, the structural formula of L-POSS crosslinking agents are as follows：
；
Modified recycling PS calculates raw material composition by weight and content is as follows：
Recycle 100 parts of PS；
5~30 parts of toughener；
5~30 parts of crosslinking masterbatch；
3~10 parts of inorganic filler.
A kind of isomerism containing L-POSS crosslinking agents is modified recycling PS, and the toughener is in POE, EVA
At least one, preferably POE.
A kind of isomerism containing L-POSS crosslinking agents is modified recycling PS, and the crosslinking agent is to contain L-
The novel silane crosslinking agent of POSS structures.
A kind of described isomerism containing L-POSS crosslinking agents is modified recycling PS, the crosslinking masterbatch be by A material,
B expects and production aqua three parts composition；
A expects composition:Recycle PS
L-POSS crosslinking agents
Initiator（Cumyl hydroperoxide (CHP)）
B expects composition：Recycle PS
Catalyst（Dibutyl tin laurate）
Antioxidant（Antioxidant 1010）
The production aqua composition is stearic acid and zinc oxide.
A kind of described isomerism containing L-POSS crosslinking agents is modified recycling PS, the inorganic filler be calcium carbonate,
At least one of talcum powder, preferably calcium carbonate.
A kind of isomerism modification recycling PS preparation methods containing L-POSS crosslinking agents, the method includes following steps
Suddenly：
A, 95 parts of A material are weighed by mass fraction, is put into extruding pelletization in double screw extruder after 4.5 parts of B material mixing, then
Again aqua is produced with 0.5 part（Stearic acid and zinc oxide molar ratio are 1:1 mixture）The uniformly mixed double screw extruder that is put into squeezes
Go out granulation and forms micro- crosslinking masterbatch；
B, micro- crosslinking masterbatch in the portions A are first put into Universalpulverizer and place into grinding in planetary ball mill until crosslinking
Until the grain size of masterbatch reaches 10~50 μm；
C, PS materials forced air drying 6~8 hours under the conditions of 80 DEG C will be recycled, by weight ratio by micro- crosslinking masterbatch, increasing
Tough dose, recycling PS, inorganic filler put into high-speed mixer and mix 4~6 minutes, so that it is uniformly mixed；
D, it is 36 that the material being uniformly mixed above-mentioned in high-speed mixer, which is added to screw slenderness ratio, rotating speed 200r/
In the double screw extruder of min, utilize the Strong shear power of twin-screw by the average grain diameter control of micro- crosslinking masterbatch in the molten state
System is uniformly mixed at 10~50 μm, while by crosslinking material with toughener, recycling PS and inorganic filler, and above-mentioned mixture is squeezed out
Granulation obtains regeneration PS.
A kind of isomerism containing L-POSS crosslinking agents is modified recycling PS preparation methods, the twin-screw extrusion
The extruder temperature of machine controls between 230 DEG C~260 DEG C.
Advantages of the present invention is with effect：
It is a kind of effective way for improving plastics mechanical property that activeness and quietness of the present invention, which is modified, and technological operation is simple and can
To produce recycled plastic in enormous quantities, meet the industrial requirement in market, therefore, this method in view of the drawbacks of the prior art
By being modified recycling PS with the isomerism cross-linking method containing L-POSS crosslinking agents, recycling PS mechanical properties are improved to reach.
Crosslinking agent of the present invention contains L-POSS and silane composition simultaneously, therefore this is that one kind having both the two performance, i.e., simultaneously
Novel crosslinker with high temperature resistant and cross-linking properties can also improve its stretching while can improving recycling PS impact strengths
Intensity improves the mechanical property of PS.
Description of the drawings
Fig. 1 is the molecular structural formula of L-POSS crosslinking agents.
Specific implementation mode
The following describes the present invention in detail with reference to examples.
Embodiment 1-3, the weight distribution ratio of each component is as shown in table 1 in each embodiment.Each component is weighed according to the ratio,
It is mixed 5 minutes in homogenizer, discharges, the raw material of mixture is placed in double screw extruder and makes material, extruder temperature
Control is between 230 DEG C~260 DEG C, rotating speed 200r/min.Batten is prepared, by corresponding standard testing（It is shown in Table 2）, performance knot
Fruit is shown in Table 3.
Table 1：Formula composition (part of embodiment 1-3）
Table 2：Mechanics Performance Testing standard
Table 3：The Mechanics Performance Testing of PS is regenerated in embodiment 1-3 and comparative example
It can be seen that from the mechanical experimental results in the embodiment 1-3 and comparative example of table 3：Female not using micro- crosslinking
When material, the addition of other modified additives can reduce the tensile property of material while improving recycling PS impact properties；And
The grain size of micro- crosslinking masterbatch obtained is crushed to after 10~50 μm and again puts into crosslinking material and recycling PS, inorganic filler etc. greatly
Shear-mixed in the double screw extruder of draw ratio, this method can also improve it while improving recycling PS impact properties
Tensile property；Realize the effect that isomerism cross-linking method is carried out at the same time recycling PS materials activeness and quietness.
The present invention is further illustrated above by specific embodiment, but these embodiments are only exemplary
, any restrictions are not constituted to protection scope of the present invention.It will be appreciated by those skilled in the art that in the spirit without departing from the present invention
In the case of protection domain, technical solutions and their implementation methods of the present invention can be carried out a variety of equivalencings, modification or
It improves, these should all fall within the scope of protection of the present invention.Protection scope of the present invention is subject to the attached claims.
Claims (6)
1. a kind of isomerism containing L-POSS crosslinking agents is modified recycling PS, which is characterized in that the structure of L-POSS crosslinking agents
Formula is as follows：
；
Modified recycling PS calculates raw material composition by weight and content is as follows：
Recycle 100 parts of PS；
5~30 parts of toughener；
5~30 parts of crosslinking masterbatch；
3~10 parts of inorganic filler；
The crosslinking masterbatch are expected by A, B expects and production aqua three parts form；
A expects composition:Recycle PS
L-POSS crosslinking agents
Initiator, the initiator are cumyl hydroperoxide CHP
B expects composition：Recycle PS
Catalyst, the catalyst are dibutyl tin laurate
Antioxidant, the antioxidant are antioxidant 1010
The production aqua composition is stearic acid and zinc oxide.
2. a kind of isomerism containing L-POSS crosslinking agents according to claim 1 is modified recycling PS, which is characterized in that
The toughener is at least one of POE, EVA.
3. a kind of isomerism containing L-POSS crosslinking agents according to claim 1 is modified recycling PS, which is characterized in that
The crosslinking agent is the silane crosslinker containing L-POSS structures.
4. a kind of isomerism containing L-POSS crosslinking agents according to claim 1 is modified recycling PS, which is characterized in that
The inorganic filler is at least one of calcium carbonate, talcum powder.
5. a kind of isomerism containing L-POSS crosslinking agents according to claim 1 is modified the preparation method of recycling PS,
It is characterized in that, the described method comprises the following steps：
A, weigh 95 parts of A material by mass fraction, extruding pelletization in double screw extruder be put into after 4.5 parts of B material mixing, then again with
0.5 part of production aqua mixing, is uniformly mixed and is put into double screw extruder extruding pelletization formation crosslinking masterbatch；The production aqua is hard
Resin acid and zinc oxide molar ratio are 1:1 mixture；
B, the crosslinking masterbatch in walking A are first put into Universalpulverizer and place into planetary ball mill grinding until crosslinking masterbatch
Until grain size reaches 10~50 μm；
C, will recycling PS materials forced air drying 6~8 hours under the conditions of 80 DEG C, by weight ratio by crosslinking masterbatch, toughener, return
Receipts PS, inorganic filler are put into high-speed mixer and are mixed 4~6 minutes, it is made uniformly to mix；
D, it is 36 that the material being uniformly mixed above-mentioned in high-speed mixer, which is added to screw slenderness ratio, and rotating speed is 200r/min's
In double screw extruder, utilize in the molten state the Strong shear power of twin-screw by the control of the average grain diameters of crosslinking masterbatch 10~
50 μm, while crosslinking masterbatch being uniformly mixed with toughener, recycling PS and inorganic filler, by above-mentioned mixture extruding pelletization
Obtain a kind of isomerism modification recycling PS containing L-POSS crosslinking agents.
6. a kind of isomerism containing L-POSS crosslinking agents according to claim 5 is modified recycling PS preparation methods,
It is characterized in that, the extruder temperature of the double screw extruder controls between 230 DEG C~260 DEG C.
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| CN201611215789.8A CN106751095B (en) | 2016-12-26 | 2016-12-26 | Isomerism containing L-POSS crosslinking agents is modified recycling PS and preparation method thereof |
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| CN201611215789.8A CN106751095B (en) | 2016-12-26 | 2016-12-26 | Isomerism containing L-POSS crosslinking agents is modified recycling PS and preparation method thereof |
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| CN106751095B true CN106751095B (en) | 2018-10-26 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109265851A (en) * | 2018-09-26 | 2019-01-25 | 德清舒华泡沫座椅有限公司 | A kind of preparation method of halogen-free flameproof polystyrene foam |
| CN109265897A (en) * | 2018-09-26 | 2019-01-25 | 德清舒华泡沫座椅有限公司 | A kind of organic-silicon-modified polystyrene and preparation method thereof |
| CN112619705B (en) * | 2019-09-24 | 2023-08-04 | 中国石油化工股份有限公司 | Alkylene oxide addition reaction catalyst and application thereof |
| CN113621194A (en) * | 2021-08-20 | 2021-11-09 | 安徽瑞琦塑胶科技有限公司 | Wear-resistant high-strength plastic particles produced by using waste plastics |
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| CN1796441A (en) * | 2004-12-30 | 2006-07-05 | 中国科学院化学研究所 | Trapezoidal organic poly sesquisiloxane and preparation method |
| CN102850490A (en) * | 2012-08-10 | 2013-01-02 | 福州大学 | Method for preparing molecularly imprinted material by POSS compound as cross-linking agent |
| CN104371188A (en) * | 2014-02-21 | 2015-02-25 | 解波 | High strength and high gloss recycled plastic and preparation method thereof |
| CN104903404A (en) * | 2013-01-09 | 2015-09-09 | 株式会社大赛璐 | Curable resin composition, and cured product of same |
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- 2016-12-26 CN CN201611215789.8A patent/CN106751095B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1796441A (en) * | 2004-12-30 | 2006-07-05 | 中国科学院化学研究所 | Trapezoidal organic poly sesquisiloxane and preparation method |
| CN102850490A (en) * | 2012-08-10 | 2013-01-02 | 福州大学 | Method for preparing molecularly imprinted material by POSS compound as cross-linking agent |
| CN104903404A (en) * | 2013-01-09 | 2015-09-09 | 株式会社大赛璐 | Curable resin composition, and cured product of same |
| CN104371188A (en) * | 2014-02-21 | 2015-02-25 | 解波 | High strength and high gloss recycled plastic and preparation method thereof |
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