CN106832929B - A kind of isomerism cross-linking method modification recycling PPS and preparation method thereof containing L-POSS crosslinking agents - Google Patents
A kind of isomerism cross-linking method modification recycling PPS and preparation method thereof containing L-POSS crosslinking agents Download PDFInfo
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- CN106832929B CN106832929B CN201611232844.4A CN201611232844A CN106832929B CN 106832929 B CN106832929 B CN 106832929B CN 201611232844 A CN201611232844 A CN 201611232844A CN 106832929 B CN106832929 B CN 106832929B
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- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
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- C08J3/00—Processes of treating or compounding macromolecular substances
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- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
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- C08J2481/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
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Abstract
A kind of isomerism cross-linking method modification recycling PPS and preparation method thereof containing L-POSS crosslinking agents, it is related to a kind of recycling PPS and preparation method thereof, recycling of the present invention by this crosslinking agent with high crosslinking temperature for heat resistance special engineered material PPS outstanding is modified, applying the cross-linking modified recycling PPS of isomerism cross-linking method, specific method of modifying simultaneously is：PPS forced air dryings will be recycled first, micro- crosslinking masterbatch made from the melting mixings extruding pelletization such as L-POSS crosslinking agents and dried recycling PPS, initiator, catalyst, antioxidant, production aqua are first put into Universalpulverizer and place into planetary ball mill the grain size ground up to micro- crosslinking masterbatch, then high-speed mixer and mixing is put into dried recycling PPS, micro- crosslinking masterbatch, toughener and inorganic filler by weight ratio, finally uses double screw extruder extruding pelletization at 180 DEG C~320 DEG C that there is the regeneration PPS of isomeric structur to obtain the final product.
Description
Technical field
The present invention relates to a kind of recycling PPS and preparation method thereof, containing the same of L-POSS crosslinking agents more particularly to a kind of
Matter isomery cross-linking method is modified recycling PPS and preparation method thereof.
Background technology
Polyphenylene sulfide（Poly Phenylene Sulfide, abbreviation PPS）Also known as polyphenylene sulfide, poly- phenylene thioether are
Thermoplastic engineering plastic containing thiophenyl on molecular backbone, synthetic method mainly have solution polymerization process and from condensation methods.PPS
Molecule is to be alternately arranged the linear polymer constituted by phenyl ring and sulphur atom, and phenyl ring is conjugated with sulphur atom in molecule, and sulphur atom
Not yet it is saturated, it is oxidized that thioether bond is made to become sulfoxide group and sulfuryl or phenyl ring and adjacent macromolecular formation oxygen bridge and be crosslinked.
In addition the thermo-oxidative stability of PPS protrudes, and continuous use temperature is up to 260 DEG C, and temperature is used continuously up to 400 DEG C in highest, and machine
Tool performance does not reduce at high temperature, therefore can be widely applied to automobile, electric, machinery industry, petrochemical industry, aerospace
Equal special dimensions, but without modified recycling PPS resin intensity difference, elongation is low, and heat resistance is declined, these disadvantages limit
Its application in many fields is made, therefore in actual use often through adjustment modifying agent and processing technology, to real
Now recycling PPS performances are advanced optimized.Mobility declines few after PPS known to inspection information is easy to be crosslinked and be crosslinked,
Therefore recycling PPS can be carried out cross-linking modified.
China Patent Publication No. is that the application for a patent for invention of CN105237936A has used a kind of cross-linking type isomerism to increase
Strong flexibilizing ABS material and preparation method thereof, this is a kind of method with isomerism crosslinking technological activeness and quietness recycled plastic,
This method is equally applicable to the modification of recycling PPS, but the decomposition temperature of the crosslinking agent cumyl peroxide used in the patent
Degree is only 120 DEG C or so, is unable to high temperature resistant, and the melting temperature mismatch of this and PPS, the initiation crosslinked effects of PPS are limited, because
This needs to find the cross-linking reaction that a kind of high temperature resistant crosslinking agent is used for PPS, applies the enhancing of isomerism cross-linking method to increase to reach
The purpose of tough recycling PPS.
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
There is good high temperature resistance, the Si-H in molecular structure can be handed over vinyl silanes for minor structure, this molecular structure
Vinyl in connection agent, which combines, forms the silane crosslinker containing L-POSS, since this crosslinking agent contains L-POSS and silane simultaneously
Composition, therefore this is a kind of novel crosslinker with high crosslinking temperature.
Invention content
The isomerism cross-linking method that the purpose of the present invention is to provide a kind of containing L-POSS crosslinking agents be modified recycling PPS and
Preparation method, the present invention returning for heat resistance special engineered material PPS outstanding by the crosslinking agent with high crosslinking temperature
It receives on modified, while applying the cross-linking modified recycling PPS of isomerism cross-linking method, be one kind effectively way for improving plastics mechanical property
Diameter, technological operation is simple and can produce recycled plastic in enormous quantities, reaches the mesh for improving recycling PPS mechanical properties
's.
The purpose of the present invention is what is be achieved through the following technical solutions：
A kind of isomerism modification recycling PPS containing L-POSS crosslinking agents, the structural formula of L-POSS crosslinking agents are as follows：
；
The composition of modified recycling PPS materials is based on mass weight part：
Recycle 100 parts of PPS；
3~20 parts of toughener；
10~30 parts of micro- crosslinking masterbatch；
5~10 parts of inorganic filler.
A kind of isomerism cross-linking method containing L-POSS crosslinking agents is modified recycling PPS, and the toughener is
At least one of POE, EVA, preferably POE.
A kind of isomerism cross-linking method containing L-POSS crosslinking agents is modified recycling PPS, and micro- crosslinking is female
Material is expected by A, B expects and production aqua three parts form；
A expects composition:Recycle PPS
L-POSS crosslinking agents
Initiator（Cumyl peroxide (DCP)）
B expects composition：Recycle PPS
Catalyst（Dibutyl tin laurate）
Antioxidant（Antioxidant 1010）
Produce aqua composition：Stearic acid and zinc oxide.
A kind of isomerism cross-linking method containing L-POSS crosslinking agents is modified recycling PPS, and the inorganic filler is
At least one of calcium carbonate, talcum powder, preferably calcium carbonate.
A kind of isomerism cross-linking method modification recycling PPS preparation methods containing L-POSS crosslinking agents, the method includes
Following steps：
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 planetary ball mill grinding until micro- friendship
Until the grain size of connection masterbatch reaches 10~50 μm；
C, PPS 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 PPS, 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 PPS and inorganic filler, and above-mentioned mixture is squeezed
Go out granulation and obtains regeneration PPS.
A kind of isomerism cross-linking method containing L-POSS crosslinking agents is modified recycling PPS preparation methods, described double
The extruder temperature of screw extruder controls between 180 DEG C~320 DEG C.
Advantages of the present invention is with effect：
Recycling of the present invention by the crosslinking agent with high crosslinking temperature for heat resistance special engineered material PPS outstanding changes
Property on, while apply the cross-linking modified recycling PPS of isomerism cross-linking method, isomerism cross-linking method of the present invention（Activeness and quietness）It is modified
It is a kind of effective way for improving plastics mechanical property, technological operation is simple and recycled plastic can be carried out to high-volume life
Production, meets the industrial requirement in market, and therefore, this method is by with containing L-POSS crosslinking agents in view of the drawbacks of the prior art
Isomerism cross-linking method is modified recycling PPS, and recycling PPS mechanical properties are improved to reach.
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.
The weight distribution ratio of each component is as shown in table 1 in embodiment 1-3 and comparative example.Each component is weighed according to the ratio, in
It is mixed 5 minutes in high-speed mixer, discharges, the raw material of mixture is placed in double screw extruder and makes material, extruder temperature control
System is between 180 DEG C~320 DEG C, rotating speed 200r/min.Batten is prepared, by corresponding standard testing（It is shown in Table 2）, results of property
It is shown in Table 3.
Table 1：Formula composition (part of embodiment 1-3 and comparative example）
Table 2：Mechanics Performance Testing standard
Table 3：The Mechanics Performance Testing of ABS 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 PPS impact properties；And
The grain size of micro- crosslinking masterbatch obtained is crushed to after 10~50 μm, micro- crosslinking masterbatch and recycling PPS etc. are put into big major diameter again
Shear-mixed in the double screw extruder of ratio, makes crosslinking material form isomerism dispersed structure with reclaimed materials, and this method is carrying
Its tensile property can also be improved while height recycling PPS impact properties；Isomerism cross-linking method is realized to recycling PPS materials
It is carried out at the same time the effect of 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 (5)
1. a kind of isomerism containing L-POSS crosslinking agents is modified recycling PPS, which is characterized in that the structure of L-POSS crosslinking agents
Formula is as follows：
；
The composition of modified recycling PPS materials is based on mass weight part：
Recycle 100 parts of PPS；
3~20 parts of toughener；
10~30 parts of crosslinking masterbatch；
5~10 parts of inorganic filler；
The crosslinking masterbatch are expected by A, B expects and production aqua three parts form；
A expects composition:Recycle PPS
L-POSS crosslinking agents
Initiator, the initiator are cumyl peroxide DCP
B expects composition：Recycle PPS
Catalyst, the catalyst are dibutyl tin laurate
Antioxidant, the antioxidant are antioxidant 1010
Produce aqua composition：Stearic acid and zinc oxide.
2. a kind of isomerism containing L-POSS crosslinking agents according to claim 1 is modified recycling PPS, feature exists
In 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 PPS, feature exists
In the inorganic filler is at least one of calcium carbonate, talcum powder.
4. a kind of isomerism containing L-POSS crosslinking agents according to claim 1 is modified the preparation method of recycling PPS,
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 PPS materials forced air drying 6~8 hours under the conditions of 80 DEG C, by weight ratio by crosslinking masterbatch, toughener,
Recycling PPS, 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 PPS and inorganic filler, by above-mentioned mixture extruding pelletization
It obtains the isomerism containing L-POSS crosslinking agents and is modified recycling PPS.
5. a kind of isomerism containing L-POSS crosslinking agents according to claim 4 is modified the preparation method of recycling PPS,
It is characterized in that, the extruder temperature of the double screw extruder controls between 180 DEG C~320 DEG C.
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| CN1058730C (en) * | 1994-01-21 | 2000-11-22 | 中国科学院化学研究所 | High-regularity ladder polyhydric sesquisiloxane and its copolymer and preparing method thereof |
| 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 |
| KR101130262B1 (en) * | 2008-12-18 | 2012-03-26 | 주식회사 효성 | Preparation of Polyethyleneterephthalate Nanocomposite Fiber with Enhanced Modulus Retention at High Temperature |
| CN102850490B (en) * | 2012-08-10 | 2014-05-21 | 福州大学 | Method for preparing molecularly imprinted material by POSS compound as cross-linking agent |
| JP5778875B2 (en) * | 2013-01-09 | 2015-09-16 | 株式会社ダイセル | Curable resin composition and cured product thereof |
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