CN102250469B - Polythioether imide and polyarylene sulfide alloy material and preparation method thereof - Google Patents
Polythioether imide and polyarylene sulfide alloy material and preparation method thereof Download PDFInfo
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- CN102250469B CN102250469B CN201010177703.3A CN201010177703A CN102250469B CN 102250469 B CN102250469 B CN 102250469B CN 201010177703 A CN201010177703 A CN 201010177703A CN 102250469 B CN102250469 B CN 102250469B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92885—Screw or gear
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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Abstract
The invention discloses a polythioether imide and polyarylene sulfide alloy material and a preparation method thereof, and the alloy material comprises the following raw materials by weight: 8%-95% of polythioether imide, 4%-9% of polyarylene sulfide, 0.01%-1% of antioxidants, and 0.01%-1% of other additives. The preparation method comprises the following steps: well mixing the raw materials, adding the raw materials into a twin screw extruder, controlling the temperature to 290-380 DEG C, performing extrusion and granulation to obtain the polythioether imide / polyarylene sulfide alloy. The preparation method of the invention prepares a polythioether imide and polyarylene sulfide alloy material with excellent comprehensive properties by a melt blending method; the alloy material has good hear resistance and shock resistance; the disadvantages of poor processing formability, alkaline corrosion intolerance, high price of polythioether imide, and poor shock resistance of polyarylene sulfide are greatly improved; and the preparation process is simple.
Description
Technical field
The present invention relates to macromolecular material and relevant preparation method's technical field, particularly a kind of Polythioetherimide and poly arylidene thio-ester alloy material and preparation method thereof.
Background technology
High-molecular polymer alloy material refers to the multicomponent system consisting of two or more macromolecular material, belongs to alloy material.Physics blend, the block copolymerization in multipolymer and the graft copolymers etc. of different polymkeric substance all belong to polymer alloy category (envelope Piao, < < polymer alloy > >, Shanghai Tongji University press, 1997; Tao Jianying, technology status and the development prospect of engineering plastics based polymer alloy, Shanghai chemical industry, 2003,02).
Polythioetherimide, because thioether bond flexible unit is incorporated in the polyimide main chain of rigidity, this base polymer is except having outstanding thermomechanical property, also having that solvability is good, melt viscosity is low and the feature of melt-processable, is a kind of very promising thermoplasticity high temperature polymeric materials.For example, publication number is that CN101463132A, CN101392055A, CN101531758A, CN101704950A and application number are the excellent over-all propertieies such as in 200910153055.5 Chinese patent application, disclosed multiple Polythioetherimide all has good heat resistance, toughness is high, melt viscosity is low, and cost is relatively low, in association areas such as resistant to elevated temperatures engineering plastics, film, sizing agent, enameled wire, porous plastics, fiber and advanced composite materials, there is good application prospect.
Compare with poly arylidene thio-ester, polyimide exists that processing forming is poor, not alkali corrosion resistance, the shortcoming such as expensive; And poly arylidene thio-ester has excellent chemical resistance, at 200 ℃, be substantially insoluble to below any solvent, good mechanical property, relatively low cost and the good advantages such as moulding processability, but its fragility is large, poor toughness, resistance to impact shock are low.Owing to all there being a large amount of aromatic nucleus on the molecular chain of polyimide and poly arylidene thio-ester, structural similarity makes them have good consistency, the processing temperature of polyimide and poly arylidene thio-ester matches simultaneously, all 300 ℃ of above processing, therefore by poly arylidene thio-ester modified polyimide, improve its processing forming and reduce costs, having caused that people pay close attention to greatly.For example, in US Patent No. 4455410 (application of General Electric company), a kind of polyetherimide/polyphenylene sulfide alloy material is disclosed, article the preparation method of polyphenylene sulfide modified polyetherimide.The sign > > of document < < polyphenylene sulfide, polysulfones and polyetherimide binary and tertiary blending system (Polymer Engineering and Science, 1991,32 (2): the blended modifier that 84-91) discloses polyphenylene sulfide and polyetherimide, blend is incompatible system, and the tensile strength of blend declines with the increase of polyphenylene sulfide content.A kind of polyimide/polyphenylene sulfide alloy material is disclosed in US Patent No. 4017555, the polyimide of not melting is carried out to modification by the blend with polyphenylene sulfide, when the content of polyphenylene sulfide reaches 40%, alloy material has obtained good machine-shaping property and good fluidity of molten, but, on the one hand because the consistency of this polyimide and polyphenylene sulfide is poor, and polyphenylene sulfide is more crisp, cause the mechanical property of polyimide to damage larger, the polyimide raw material price used is on the other hand more expensive, make the cost value of polyimide/poly arylidene thio-ester alloy material of preparation higher.
Summary of the invention
The invention provides a kind of Polythioetherimide and poly arylidene thio-ester alloy material, it has good resistance toheat, has the mechanical property that high-modulus, high strength, high impact etc. are excellent simultaneously.
The present invention also provides the preparation method of a kind of Polythioetherimide and poly arylidene thio-ester alloy material, and its preparation technology is simple, is suitable for suitability for industrialized production.
Polythioetherimide and a poly arylidene thio-ester alloy material, be comprised of the raw material of following weight percent:
Polythioetherimide 8%~95%;
Poly arylidene thio-ester 4%~90%;
Oxidation inhibitor 0.01%~1%;
Other auxiliary agent 0.01%~1%.
Described Polythioetherimide has as shown in the formula the structural formula shown in I:
In formula I, m and n represent respectively the polymerization degree, the integer that n is 1~20000; , desirable 10 to 10000 integer or more integer;
M is 0~20000 integer; Desirable 10 to 10000 integer or more integer; When m=0, it is the Polythioetherimide of homopolymerization; When m > 0, it is the Polythioetherimide of copolymerization;
In Polythioetherimide, the position of thioether bond on phthalimide structural unit is 3-position or the 4-position of phthalimide structural unit;
A for replace or unsubstituted aliphatic group, replacement or unsubstituted aromatic group in a kind of;
X is fragrant sulfone structural unit or aromatic ketone structural unit.
As preferably:
Described aliphatic group is selected from C
1~C
10aliphatic chain alkyl or C
3~C
10cycloaliphatic ring alkyl in a kind of or at least two kinds of groups that connect with C-C key and form.Described aromatic base is selected from C
6~C
30aromatic group, further preferably C
6~C
30benzene series aromatic group.For example, can select
a kind of or at least two kinds of groups that connect with C-C key and form in them.
Described fragrant sulfone structural unit has as shown in the formula the structural formula shown in the structural formula shown in the structural formula shown in II, formula III or formula IV:
In formula II, formula III or formula IV, substituting group M is H, SO
3li, SO
3na, SO
3k or SO
3h; The position relationship of substituting group M and thioether bond is ortho position, a position or contraposition;
In formula IV, Z is selected from a kind of in following group:
wherein, R is selected from a kind of in following group:
a or b are 1~6 integer.
Described aromatic ketone structural unit has as shown in the formula the structural formula shown in the structural formula shown in the structural formula shown in the structural formula shown in V, formula VI, the structural formula shown in formula VII, formula VIII, the structural formula shown in formula IX, formula X or the structural formula shown in formula XI:
In formula V, the integer that K is 1~20; R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8can be the same or different, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8independently be selected from separately H, CH
3, (CH
2) rCH
3, CN, OH, COOH, SO
3h, SO
3na, wherein, the integer that r is 1~30;
In formula VI, k, k ', h, h ' can be the same or different, and k, k ', h, h ' are independently selected from 1~20 integer separately; R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8can be the same or different, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8independently be selected from separately H, CH
3, (CH
2) rCH
3, CN, OH, COOH, SO
3h, SO
3na, wherein, the integer that r is 1~30;
In formula VII, k, k ', h, h ' can be the same or different, and k, k ', h, h ' are independently selected from 1~20 integer separately; R
1, R
2, R
3, R
4, R
5, R
6can be the same or different, R
1, R
2, R
3, R
4, R
5, R
6independently be selected from separately H, CH
3, (CH
2) rCH
3, CN, OH, COOH, SO
3h, SO
3na, wherein, the integer that r is 1~30;
In formula VIII, the integer that k is 1~20; R
1, R
2, R
3, R
4, R
5, R
6can be the same or different, R
1, R
2, R
3, R
4, R
5, R
6independently be selected from separately H, CH
3, (CH
2) rCH
3, CN, OH, COOH, SO
3h, SO
3na, wherein, the integer that r is 1~30;
In formula IX, the integer that k, k ' they are 1~20; R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8can be the same or different, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8independently be selected from separately H, CH
3, (CH
2) rCH
3, CN, OH, COOH, SO
3h, SO
3na, two substituent positions that are labeled as on the phenyl ring of Mid are contraposition or a position; Wherein, the integer that r is 1~30;
In formula X, k, h, h ' can be the same or different, and k, h, h ' are independently selected from 1~20 integer separately; R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8can be the same or different, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8independently be selected from separately H, CH
3, (CH
2) rCH
3, CN, OH, COOH, SO
3h, SO
3na, wherein, the integer that r is 1~30;
In formula XI, the integer that k is 1~20; R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10can be the same or different, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10independently be selected from separately H, CH
3, (CH
2) rCH
3, CN, OH, COOH, SO
3h, SO
3na, wherein, the integer that r is 1~30.Described poly arylidene thio-ester has as shown in the formula the structural formula shown in i:
In formula i, the integer that d is 1~5000, desirable 10 to 1000 integer or more integer; R ' is selected from and replaces or unsubstituted aromatic group.
Described oxidation inhibitor is selected from Hinered phenols antioxidant, phosphite ester kind antioxidant, containing one or more in sulfur type antioxidant and metallic ion passivation agent.
The composite antioxidant that described multiple oxidation inhibitor forms can be selected the composite antioxidant of Hinered phenols antioxidant and phosphite ester kind antioxidant, as one or more in the commercially available prod such as composite antioxidant 215, composite antioxidant 225, composite antioxidant 561, composite antioxidant 900.
Described Hinered phenols antioxidant can be selected one or more in the commercially available prod such as antioxidant 1010, antioxidant 1076, antioxidant 3114, oxidation inhibitor 1098, antioxidant BHT, oxidation inhibitor 702, oxidation inhibitor 1330, oxidation inhibitor 1135.
Described phosphite ester kind antioxidant can be selected one or more in the commercially available prod such as irgasfos 168, antioxidant TNP, oxidation inhibitor 626, antioxidant 618.
Described containing optional one or more with in the commercially available prod such as anti-oxidant DLTP, oxidation inhibitor DLTDP, oxidation inhibitor DSTP, oxidation inhibitor DSTDP of sulfur type antioxidant.
Described metallic ion passivation agent can be selected one or more in the commercially available prod such as the vapour Bagong IrganoxMD-1024 of department, the NouguardXL-1 of Uniroyal,Inc..
Other described auxiliary agent comprises one or more in processing aid, thermo-stabilizer, lubricant, photostabilizer or ultraviolet absorbers.
Described photostabilizer can be selected one or more in the commercially available prod such as resistance amine photostabilizer 770, resistance amine photostabilizer 944, resistance amine photostabilizer 622, resistance amine photostabilizer 783, resistance amine photostabilizer HALS.
Described lubricant can be selected the commercially available prod such as pentaerythritol stearate PETS-3 or pentaerythritol stearate PETS-4.
Described ultraviolet absorbers can be selected one or more in the commercially available prod such as UV-531, UV-326, UV-327.
Described processing aid and thermo-stabilizer can be selected the conventional processing aid in this area and thermo-stabilizer.
The preparation method of described Polythioetherimide and poly arylidene thio-ester alloy material, comprises the following steps:
(1) first by Polythioetherimide, poly arylidene thio-ester respectively at 130 ℃~180 ℃ vacuum-dryings (more than 5 hours);
(2) by dried Polythioetherimide and poly arylidene thio-ester, and oxidation inhibitor is dry mixed in room temperature with other auxiliary agent, after mixing, put in twin screw extruder, by twin screw extruder extruding pelletization, make Polythioetherimide and poly arylidene thio-ester alloy material;
In described twin screw extruder: district's temperature is 290 ℃~320 ℃; Two district's temperature are 320 ℃~340 ℃; Three district's temperature are 340 ℃~360 ℃; Four district's temperature are 350 ℃~380 ℃; Five district's temperature are 330 ℃~360 ℃; Six district's temperature are 320 ℃~340 ℃; Head temperature is 280 ℃~310 ℃; 300 revs/min~450 revs/min of engine speeds.
Described twin screw extruder can adopt the twin screw extruder of this area routine.
Compared with prior art, the invention has the advantages that:
1, Polythioetherimide of the present invention and poly arylidene thio-ester alloy material, cost is low, consistency is good, has improved that Polythioetherimide processing forming is poor, not alkali corrosion resistance, the shortcoming such as price is more expensive and poly arylidene thio-ester impact resistance is poor, elongation at break is lower.
2, Polythioetherimide of the present invention and poly arylidene thio-ester alloy material, there is good resistance toheat, high-modulus, high strength, high impact and the outstanding excellent over-all propertieies such as flame retardant properties, its tensile modulus can reach 2.0GPa~4.0GPa, tensile strength can reach 60MPa~200MPa, elongation at break can reach 5.0%~50.0%, and non-notch resistance to impact shock can reach 60KJ/m
2~200KJ/m
2, resistance rank reaches UL94-V-0 rank, is 93 ℃ floods respectively 24 hours in 30% (mass percentage concentration) aqueous sodium hydroxide solution and water in temperature, and stretching strength retentivity is respectively 60%~95% and 65%~96%.
3, the preparation method of Polythioetherimide of the present invention and poly arylidene thio-ester alloy material is simple to operate, cost is low, is suitable for suitability for industrialized production.
4, the polyimide adopting is Polythioetherimide cheaply, this alloy has more price advantage compared with its like product, product cost performance is higher, can bring higher economic benefit and social benefit, in association areas such as thermostability engineering plastic, film, porous plastics, fiber and advanced composite materials, have good application prospect.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail, it is important to point out that this example, only for the present invention is further detailed, can not be interpreted as limiting the scope of the invention.Person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of foregoing invention.
In the raw material of the alloy material of the following example forms, Polythioetherimide is this laboratory self-control, and preparation method is that CN101463132A, CN101392055A, CN101531758A, CN101704950A and application number are the preparation method of disclosed multiple Polythioetherimide in 200910153055.5 Chinese patent application by publication number.
Choosing respectively the Polythioetherimide of homopolymerization, is 0.53dL/g 30 ℃ of logarithmic viscosity numbers of measuring in meta-cresol, and structural formula is suc as formula shown in (ii):
Containing the common Polythioetherimide of fragrant sulfone structure, 30 ℃ of limiting viscosities in meta-cresol are 0.65dL/g, and 350 ℃ of melt viscosities are 4000Pas, and structural formula is suc as formula shown in (iii):
With containing aromatic ketone structure Polythioetherimide altogether, 30 ℃ of limiting viscosities in meta-cresol are 0.55dL/g, 350 ℃ of melt viscosities be 3800Pas structural formula suc as formula shown in (iv):
It is research object that poly arylidene thio-ester is selected wherein the most representative polyphenylene sulfide, and structural formula is as follows:
Above-mentioned polyphenylene sulfide is the injection grade polyphenylene sulfide that U.S. Cheron-Phillips company produces, and molecular weight is greater than 30000, and commodity are called Ryton PPS.
Oxidation inhibitor is Hinered phenols, phosphorous acid esters, contains one or more in sulfur type antioxidant and metallic ion passivation agent, and Hinered phenols antioxidant is as Switzerland Ciba company antioxidant 1010,1076; Phosphite ester kind antioxidant is as Switzerland Ciba company irgasfos 168, TNP; Contain sulfur type antioxidant as the DLTP of Switzerland Ciba company, DSTP; The IrganoxMD-1024 of metallic ion passivation Ji Ru Switzerland Ciba company.
Other auxiliary agent comprises processing aid, thermo-stabilizer, photostabilizer, lubricant etc., and lubricant is as pentaerythritol stearate PETS-3, the PETS-4 of Italian FACI company; Resistance amine photostabilizer is as Switzerland Ciba company 770,944; Ultraviolet absorbers is as Milan, Nanjing UV-531 of Chemical Co., Ltd. or UV-326.
Embodiment 1
91.28 grams of the 4-chloro-benzoic anhydrides (0.5mol) that add in the 1L of dried and clean there-necked flask, 500 milliliters of N, N-N,N-DIMETHYLACETAMIDE (DMAc), after stirring and dissolving, add 49.56 grams of (0.25mol) 4,4 '-dichloro-base ditane (MDA), be heated to 80 ℃ of reactions 2 hours, be warmed up to again 130 ℃ of reactions 16 hours, then concentrating under reduced pressure is to approximately 200 milliliters, be poured in 3 premium on currency, filter to obtain white solid, distillation washing three times for filter cake, 120 ℃ of vacuum dryings obtain 116 grams of two chlorine monomer crude products, yield 88%.After crude product vacuum fusion for next step polyreaction.
Under nitrogen atmosphere, in 500 milliliters of there-necked flasks of dried and clean, add 26.37 grams (0.05mol) above-mentioned pair of chlorine monomer, 2.30 grams of (0.05mol) anhydrous lithium sulfides, 200 milliliters of METHYLPYRROLIDONEs (NMP), be warming up to 170 ℃ of reactions 8 hours, be warming up to 170 ℃ of reactions 8 hours, cool to room temperature is slowly poured reaction solution in 2L water and is stirred 12 hours, filter, 90% (concentration expressed in percentage by volume) ethanol extracting 24 hours for filter cake, after 150 ℃ of vacuum dryings, obtain 21.0 grams of faint yellow polyimide powders, yield 86%.The logarithmic viscosity number of measuring in 30 ℃, the meta-cresol of concentration 0.5dL/g is 0.37dL/g.IR (KBr): 3438,1778,1716,1606,1378,741cm-1, structural formula is suc as formula the equal Polythioetherimide shown in (ii).
Embodiment 2
In 250ml there-necked flask, add 5.29g (0.01mol) 4,4 '-bis-(4-chloro imide) phenyl ether, 2.87g (0.01mol) 4 ', 4-dichloro diphenyl sulfone, 0.67g (0.021mol) sulphur, 5.67g (0.063) trioxymethylene, 1.68g sodium hydroxide, 0.25g calcium chloride, after logical nitrogen deoxygenation three times, add 100mlN-methyl-2-pyrrolidone (mass percent is 8%), be heated to 150 ℃ of reactions after 5 hours, after cool to room temperature, add after 0.11g chlorobenzene and reheat 180 ℃ of reactions 3 hours, reaction solution cool to room temperature is carried out to aftertreatment.
Reaction solution is poured into lentamente in methyl alcohol and stirred 2 hours, after filtering, use water boil 1 hour, filter, filter cake is got up by filter paper packet, with the extracting 24 hours in apparatus,Soxhlet's of the mixing solutions (volume ratio 1: 1) of ethanol and acetone, then by resulting polymers in vacuum drying oven 200 ℃ dry 48 hours.
30 ℃ of the resulting polymers limiting viscosity in meta-cresol is 0.65dL/g, and 350 ℃ of melt viscosities are 4000Pas, and structural formula is suc as formula the common Polythioetherimide shown in (iii).
Embodiment 3
In 250ml there-necked flask, add 5.29g (0.01mol) 4,4 '-bis-(4-chloro imide) phenyl ether, 2.51g (0.01mol) 4 ' 4-bis-chloro benzophenones, 0.67g (0.021mol) sulphur, 5.67g (0.063) trioxymethylene, 1.68g sodium hydroxide, 0.50g calcium chloride, after logical nitrogen deoxygenation three times, add 100mlN-methyl-2-pyrrolidone (solid content: 8%), be heated to 150 ℃ of reactions after 5 hours, after adding 0.11g chlorobenzene after cool to room temperature, reheat 180 ℃ of reactions 3 hours, reaction solution cool to room temperature is carried out to aftertreatment.
Reaction solution is poured into lentamente in methyl alcohol and stirred 2 hours, after filtering, use water boil 1 hour, filter, by filter paper packet for filter cake, with the mixing solutions (volume ratio 1: 1) of ethanol and acetone, in Soxhlet, extract wherein extracting 24 hours, then by resulting polymers in vacuum drying oven 200 ℃ dry 48 hours.
30 ℃ of the resulting polymers limiting viscosity in meta-cresol is 0.55dL/g, and 350 ℃ of melt viscosities are 4000Pas, and structural formula is suc as formula the common Polythioetherimide shown in (iv).
Embodiment 4:
Equal Polythioetherimide shown in the formula first embodiment 1 being made (ii), polyphenylene sulfide respectively in vacuum drying oven in 130 ℃ of vacuum-dryings 5 hours.
Dried equal Polythioetherimide (ii), polyphenylene sulfide, antioxidant 1010, irgasfos 168 and resistance amine photostabilizer 944 (Switzerland Ciba company) are mixed to 3min in mixing tank (50rmp) under room temperature, in mixture, all the weight percent of Polythioetherimide (ii) is 74.25%, the weight percent of polyphenylene sulfide is 24.75%, the weight percent of antioxidant 1010 is 0.3%, the weight percent of irgasfos 168 is 0.2%, and the weight percent of resistance amine photostabilizer 944 is 0.5%.Material after mixing is joined in the hopper of twin screw extruder, through melt blending, extruding pelletization, makes Polythioetherimide and poly arylidene thio-ester alloy material.
Wherein the processing conditions of twin screw extruder is: 330 ℃ of district's temperature 315 ℃, bis-district's temperature 330 ℃, tri-district's temperature 345 ℃, tetra-district's temperature 355 ℃, five district's temperature 350 ℃, six district's temperature, 315 ℃ of head temperatures, 300 revs/min of engine speeds.
Embodiment 5:
Equal Polythioetherimide shown in the formula first embodiment 1 being made (ii), polyphenylene sulfide respectively in vacuum drying oven in 160 ℃ of vacuum-dryings 4 hours.
By dried equal Polythioetherimide (ii), polyphenylene sulfide, antioxidant 1010, irgasfos 168, resistance amine photostabilizer 944 (Switzerland Ciba companies) and UV-531 (Milan, Nanjing Chemical Co., Ltd.) mix 3min in mixing tank (50rmp) under room temperature, in mixture, all the weight percent of Polythioetherimide (ii) is 49.5%, the weight percent of polyphenylene sulfide is 49.5%, the weight percent of antioxidant 1010 is 0.3%, the weight percent of irgasfos 168 is 0.2%, the weight percent of resistance amine photostabilizer 944 is 0.2%, the weight percent of UV-531 is 0.3%.Material after mixing is joined in the hopper of twin screw extruder, through melt blending, extruding pelletization, makes Polythioetherimide and poly arylidene thio-ester alloy material.
Wherein the processing conditions of twin screw extruder is: 320 ℃ of district's temperature 310 ℃, bis-district's temperature 315 ℃, tri-district's temperature 320 ℃, tetra-district's temperature 330 ℃, five district's temperature 330 ℃, six district's temperature, 305 ℃ of head temperatures, 400 revs/min of engine speeds.
Embodiment 6:
Equal Polythioetherimide shown in the formula first embodiment 1 being made (ii), polyphenylene sulfide respectively in vacuum drying oven in 150 ℃ of vacuum-dryings 5 hours.
By dried equal Polythioetherimide (ii), polyphenylene sulfide, antioxidant 1010, irgasfos 168, resistance amine photostabilizer 944 (Switzerland Ciba companies) and UV-326 (Milan, Nanjing Chemical Co., Ltd.) mix 3min in mixing tank (50rmp) under room temperature, in mixture, all the weight percent of Polythioetherimide (ii) is 24.75%, the weight percent of polyphenylene sulfide is 74.25%, the weight percent of antioxidant 1010 is 0.3%, the weight percent of irgasfos 168 is 0.2%, the weight percent of resistance amine photostabilizer 944 is 0.2%, the weight percent of UV-326 is 0.3%.Material after mixing is joined in the hopper of twin screw extruder, through melt blending, extruding pelletization, makes Polythioetherimide and poly arylidene thio-ester alloy material.
Wherein the processing conditions of twin screw extruder is: 320 ℃ of district's temperature 310 ℃, bis-district's temperature 315 ℃, tri-district's temperature 320 ℃, tetra-district's temperature 330 ℃, five district's temperature 330 ℃, six district's temperature, 305 ℃ of head temperatures, 450 revs/min of engine speeds.
Embodiment 7:
Equal Polythioetherimide shown in the formula first embodiment 1 being made (ii), polyphenylene sulfide respectively in vacuum drying oven in 140 ℃ of vacuum-dryings 5 hours.
Dried equal Polythioetherimide (ii), polyphenylene sulfide, antioxidant 1010, irgasfos 168 and UV-326 (Milan, Nanjing Chemical Co., Ltd.) are mixed to 3min in mixing tank (50rmp) under room temperature, the weight percent that in mixture, all the weight percent of Polythioetherimide (ii) is 9.9%, the weight percent of polyphenylene sulfide is 89.1%, the weight percent of antioxidant 1010 is 0.3%, the weight percent of irgasfos 168 is 0.2%, UV-326 is 0.5%.Material after mixing is joined in the hopper of twin screw extruder, through melt blending, extruding pelletization, makes Polythioetherimide and poly arylidene thio-ester alloy material.
Wherein the processing conditions of twin screw extruder is: 320 ℃ of district's temperature 310 ℃, bis-district's temperature 315 ℃, tri-district's temperature 320 ℃, tetra-district's temperature 330 ℃, five district's temperature 330 ℃, six district's temperature, 305 ℃ of head temperatures, 400 revs/min of engine speeds.
Embodiment 8:
Shown in the formula first embodiment 2 being made (iii) containing the common Polythioetherimide of sulfone structure, polyphenylene sulfide respectively in vacuum drying oven in 150 ℃ of vacuum-dryings 5 hours.
By dried Polythioetherimide (iii) altogether, polyphenylene sulfide, antioxidant 1010, irgasfos 168, pentaerythritol stearate PETS-3 (Italian FACI company) and UV-326 (Milan, Nanjing Chemical Co., Ltd.) mix 3min in mixing tank (50rmp) under room temperature, in mixture, the weight percent of Polythioetherimide (iii) is 24.75% altogether, the weight percent of polyphenylene sulfide is 74.25%, the weight percent of antioxidant 1010 is 0.3%, the weight percent of irgasfos 168 is 0.2%, the weight percent of pentaerythritol stearate PETS-3 is 0.1%, the weight percent of UV-326 is 0.4%.Material after mixing is joined in the hopper of twin screw extruder, through melt blending, extruding pelletization, makes Polythioetherimide and poly arylidene thio-ester alloy material.
Wherein the processing conditions of twin screw extruder is: 320 ℃ of district's temperature 310 ℃, bis-district's temperature 315 ℃, tri-district's temperature 320 ℃, tetra-district's temperature 330 ℃, five district's temperature 330 ℃, six district's temperature, 305 ℃ of head temperatures, 350 revs/min of engine speeds.
Embodiment 9:
Shown in the formula first embodiment 3 being made (iv) containing the common Polythioetherimide of ketone structure, polyphenylene sulfide respectively in vacuum drying oven in 150 ℃ of vacuum-dryings 5 hours.
By dried Polythioetherimide (iv) altogether, polyphenylene sulfide, antioxidant 1010, irgasfos 168, pentaerythritol stearate PETS-3 (Italian FACI company) and UV-326 (Milan, Nanjing Chemical Co., Ltd.) (50rmp) in mixing tank mix 3min under room temperature, in mixture, the weight percent of Polythioetherimide (iv) is 74.25% altogether, the weight percent of polyphenylene sulfide is 24.75%, the weight percent of antioxidant 1010 is 0.3%, the weight percent of irgasfos 168 is 0.2%, the weight percent of pentaerythritol stearate PETS-3 is 0.1%, the weight percent of UV-326 is 0.4%, material after mixing is joined in the hopper of twin screw extruder, through melt blending, extruding pelletization, make Polythioetherimide and poly arylidene thio-ester alloy material.
Wherein the processing conditions of twin screw extruder is: 320 ℃ of district's temperature 310 ℃, bis-district's temperature 315 ℃, tri-district's temperature 320 ℃, tetra-district's temperature 330 ℃, five district's temperature 330 ℃, six district's temperature, 305 ℃ of head temperatures, 350 revs/min of engine speeds.
Comparative example 1:
Equal Polythioetherimide shown in the formula first embodiment 1 being made (ii) in vacuum drying oven in 130 ℃ of vacuum-dryings 5 hours.
Dried equal Polythioetherimide (ii), antioxidant 1010, irgasfos 168 and resistance amine photostabilizer 770 (Switzerland Ciba company) are mixed to 5min in mixing tank (50rmp) under room temperature, in mixture, all the weight percent of Polythioetherimide (ii) is 99%, the weight percent of antioxidant 1010 is 0.3%, the weight percent of irgasfos 168 is 0.2%, and the weight percent of resistance amine photostabilizer 770 is 0.5%.Material after mixing is joined in the hopper of twin screw extruder, through melt blending, extruding pelletization, makes Polythioetherimide material.
Wherein the processing conditions of twin screw extruder is: 330 ℃ of district's temperature 315 ℃, bis-district's temperature 330 ℃, tri-district's temperature 345 ℃, tetra-district's temperature 355 ℃, five district's temperature 350 ℃, six district's temperature, 310 ℃ of head temperatures, 300 revs/min of engine speeds.
Comparative example 2
Shown in the formula first embodiment 2 being made (iii) containing the common Polythioetherimide (iii) of sulfone structure in vacuum drying oven in 130 ℃ of vacuum-dryings 5 hours.
Dried Polythioetherimide (iii), antioxidant 1010, irgasfos 168 and resistance amine photostabilizer 770 (Switzerland Ciba company) are altogether mixed to 5min in mixing tank (50rmp) under room temperature, in mixture, altogether the weight percent of Polythioetherimide (iii) is 99%, the weight percent of antioxidant 1010 is 0.3%, the weight percent of irgasfos 168 is 0.2%, and the weight percent of resistance amine photostabilizer 770 is 0.5%.Material after mixing is joined in the hopper of twin screw extruder, through melt blending, extruding pelletization, makes Polythioetherimide material.
Wherein the processing conditions of twin screw extruder is: 330 ℃ of district's temperature 315 ℃, bis-district's temperature 330 ℃, tri-district's temperature 345 ℃, tetra-district's temperature 355 ℃, five district's temperature 350 ℃, six district's temperature, 310 ℃ of head temperatures, 300 revs/min of engine speeds.
Comparative example 3
Shown in the formula first embodiment 3 being made (iv) containing the common Polythioetherimide (iv) of ketone structure in vacuum drying oven in 130 ℃ of vacuum-dryings 5 hours.
Dried Polythioetherimide (iv), antioxidant 1010, irgasfos 168 and resistance amine photostabilizer 770 (Switzerland Ciba company) are altogether mixed to 5min in mixing tank (50rmp) under room temperature, in mixture, altogether the weight percent of Polythioetherimide (iii) is 99%, the weight percent of antioxidant 1010 is 0.3%, the weight percent of irgasfos 168 is 0.2%, and the weight percent of resistance amine photostabilizer 770 is 0.5%.Material after mixing is joined in the hopper of twin screw extruder, through melt blending, extruding pelletization, makes Polythioetherimide material.
Wherein the processing conditions of twin screw extruder is: 330 ℃ of district's temperature 315 ℃, bis-district's temperature 330 ℃, tri-district's temperature 345 ℃, tetra-district's temperature 355 ℃, five district's temperature 350 ℃, six district's temperature, 310 ℃ of head temperatures, 300 revs/min of engine speeds.
In order to characterize the fluidity of molten of Polythioetherimide and polyphenylene sulfide alloy, in BrabenderPlasticorder Mixer instrument, carry out the test of torque-proportion relation.
By equal Polythioetherimide (ii), polyphenylene sulfide is respectively by the ratio of following different weight percent: 100/0, 80/20, 70/30, 60/40, 50/50, 40/60, 30/70, 20/80 weighing, be pre-mixed respectively 2h, the material mixing is joined and in Brabender torque rheometer, carries out melt blending, wherein the test conditions of melt blending is: blending temperature is 330 ℃, rotor speed is 30 revs/min, until moment of torsion reaches balance, test period is about 15 minutes, measure the torque rheology of Polythioetherimide and polyphenylene sulfide alloy, test result is in Table 1:
The alloy torque of table 1 Polythioetherimide/polyphenylene sulfide and proportion relation
Equal Polythioetherimide/polyphenylene sulfide | Torque (N.m) | Polythioetherimide/polyphenylene sulfide | Torque (N.m) |
100/0 | 21.3 | 50/50 | 5.1 |
80/20 | 15.4 | 40/60 | 4.4 |
70/30 | 9.8 | 30/70 | 3.2 |
60/40 | 6.8 | 20/80 | 2.5 |
Because torque and its melt viscosity of polymkeric substance are proportional, so torque reduction means that polymer malt viscosity reduces.As can be seen from Table 1, along with the content of polyphenylene sulfide in alloy increases, the torque of Polythioetherimide and polyphenylene sulfide alloy declines to a great extent, and its melt viscosity significantly reduces.Relatively pure Polythioetherimide, when polyphenylene sulfide content is respectively 20% and 30%, torque has reduced respectively 27.7% and 54.0%.So show from torque rheology test result, can significantly reduce the melt viscosity of Polythioetherimide by adding polyphenylene sulfide, thereby improve significantly its moulding processability.
By the prepared alloy material of above-described embodiment 1~6, and the prepared material of comparative example 1~3 carries out Performance Detection, the results are shown in Table 2 and table 3:.
Tensile strength detects according to GB GB/T1040, and draw speed is 10mm/min.Specimen types is I type, batten size (mm): 170 (length) * (20 ± 0.2) (end width) * (4 ± 0.2) (thickness).
Flexural strength and modulus in flexure detect according to GB GB 9341/T.Specimen size (mm): (80 ± 2) * (10 ± 0.2) * (4 ± 0.2), rate of bending is 20mm/min.
Non-incision shock strength is tested by GB/T 1843-1996 standard.Specimen types is 1 type specimen size (mm): (80 ± 2) * (10 ± 0.2) * (4 ± 0.2).
Heat-drawn wire performance detects according to GB GB 1634-79.Specimen size (mm): (80 ± 2) * (10 ± 0.2) * (4 soil 0.2).
Vertical combustion performance detects according to GB GB/T2408-96.Specimen size (mm): (130 ± 2) * (13 ± 0.2) * (3.2 ± 0.2).
Table 2
Weight percent forms | Comparative example 1 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 |
Equal Polythioetherimide (%) | 99 | 74.25 | 49.5 | 24.75 | 9.9 |
Polyphenylene sulfide (%) | 0 | 24.75 | 49.5 | 74.25 | 89.1 |
1010(%) | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
168(%) | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
Other auxiliary agent (%) | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
The performance test results | |||||
Tensile modulus (MPa) | 3212 | 3142 | 3093 | 2953 | 2921 |
Tensile strength (MPa) | 112.2 | 103.6 | 94.3 | 76.3 | 68.2 |
Elongation at break (%) | 12.3 | 9.6 | 6.3 | 5.1 | 4.2 |
Modulus in flexure (MPa) | 3475 | 3243 | 3254 | 3138 | 3106 |
Flexural strength (MPa) | 172.5 | 161.6 | 131.4 | 118.6 | 112.3 |
Unnotched impact strength (KJ/m 2) | 123.3 | 114.3 | 83.2 | 62.4 | 59.3 |
Heat-drawn wire (℃) | 235 | 209 | 172 | 12.3 | 93.6 |
Flame retardant properties | V-0 | V-0 | V-0 | V-0 | V-0 |
As can be seen from Table 2, in Polythioetherimide and polyphenylene sulfide alloy material, when Polythioetherimide is matrix, alloy material mechanical property is than the not too large variation of pure Polythioetherimide.But, when the content of polyphenylene sulfide surpasses 50% in alloy material, the mechanical property of alloy has declined much with respect to pure Polythioetherimide, this is because the mechanical property of alloy material is mainly reflected on matrix, therefore when polyphenylene sulfide is matrix, mechanical property, especially impact strength decreased a lot.
Table 3
Weight percent forms | Comparative example 2 | Embodiment 8 | Comparative example 3 | Embodiment 9 |
Common Polythioetherimide (%) containing sulfone structure | 99 | 74.25 | 0 | 0 |
Copolymerization thioether imines (%) containing ketone structure | 0 | 0 | 99 | 74.25 |
Polyphenylene sulfide (%) | 0 | 24.75 | 0 | 24.75 |
1010(%) | 0.3 | 0.3 | 0.3 | 0.3 |
168(%) | 0.2 | 0.2 | 0.2 | 0.2 |
Other auxiliary agent (%) | 0.5 | 0.5 | 0.5 | 0.5 |
The performance test results | ||||
Tensile modulus (MPa) | 3406 | 3200 | 3416 | 3267 |
Tensile strength (MPa) | 134.5 | 120.3 | 132.1 | 118.6 |
Elongation at break (%) | 15.6 | 13.2 | 14.9 | 12.5 |
Modulus in flexure (MPa) | 3783 | 3512 | 3706 | 3473 |
Flexural strength (MPa) | 196.2 | 175.3 | 191.3 | 174.6 |
Unnotched impact strength (KJ/m 2) | 135.2 | 125.1 | 137.2 | 126.3 |
Heat-drawn wire (℃) | 240.3 | 223 | 241.1 | 200 |
Flame retardant properties | V-0 | V-0 | V-0 | V-0 |
From the result of table 1, table 2 and table 3, can draw, adopt Progress On Polyphenylene Sulfide Blends Polythioetherimide, high temperature resistant and the excellent mechanical property that has not only kept Polythioetherimide, improves its processing forming thereby can also reduce significantly its melt viscosity.Meanwhile, because the polyimide adopting in this alloy is Polythioetherimide cheaply, so this alloy is compared its like product in price, have more competitive power, the cost performance of product is higher.Polythioetherimide prepared by the present invention and polyphenylene sulfide alloy have excellent over-all properties, can well serve the fields such as aerospace, microelectronics, automobile, electric, new forms of energy.
Claims (9)
1. Polythioetherimide and a poly arylidene thio-ester alloy material, by the raw material of following weight percent, made:
Polythioetherimide 8%~95%;
Poly arylidene thio-ester 4%~90%;
Oxidation inhibitor 0.01%~1%;
Other auxiliary agent 0.01%~1%;
Described Polythioetherimide has as shown in the formula the structural formula shown in I:
In formula I, m and n represent respectively the polymerization degree, the integer that n is 1~20000; M is 0~20000 integer;
In Polythioetherimide, the position of thioether bond on phthalimide structural unit is 3-position or the 4-position of phthalimide structural unit;
A is unsubstituted aromatic group;
X is fragrant sulfone structural unit or aromatic ketone structural unit.
2. Polythioetherimide according to claim 1 and poly arylidene thio-ester alloy material, is characterized in that: described aromatic group is selected from C
6~C
30aromatic group.
4. Polythioetherimide according to claim 1 and poly arylidene thio-ester alloy material, is characterized in that: described fragrant sulfone structural unit has as shown in the formula the structural formula shown in the structural formula shown in II, formula III or the structural formula shown in formula IV:
In formula II, formula III or formula IV, substituting group M is H, SO
3li, SO
3na, SO
3k or SO
3h; The position relationship of substituting group M and thioether bond is ortho position, a position or contraposition;
5. Polythioetherimide according to claim 1 and poly arylidene thio-ester alloy material, is characterized in that: described aromatic ketone structural unit has as shown in the formula the structural formula shown in the structural formula shown in the structural formula shown in the structural formula shown in V, formula VI, the structural formula shown in formula VII, formula VIII, the structural formula shown in formula IX, formula X or the structural formula shown in formula XI:
Or
In formula V, the integer that K is 1~20; R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8can be the same or different, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8independently be selected from separately H, CH
3, (CH
2) rCH
3, CN, OH, COOH, SO
3h, SO
3na wherein, the integer that r is 1~30;
In formula VI, k, k ', h, h ' can be the same or different, and k, k ', h, h ' are independently selected from 1~20 integer separately; R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8can be the same or different, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8independently be selected from separately H, CH
3, (CH
2) rCH
3, CN, OH, COOH, SO
3h, SO
3na, wherein, the integer that r is 1~30;
In formula VII, k, k ', h, h ' can be the same or different, and k, k ', h, h ' are independently selected from 1~20 integer separately; R
1, R
2, R
3, R
4, R
5, R
6can be the same or different, R
1, R
2, R
3, R
4, R
5, R
6independently be selected from separately H, CH
3, (CH
2) rCH
3, CN, OH, COOH, SO
3h, SO
3na, wherein, the integer that r is 1~30;
In formula VIII, the integer that k is 1~20; R
1, R
2, R
3, R
4, R
5, R
6can be the same or different, R
1, R
2, R
3, R
4, R
5, R
6independently be selected from separately H, CH
3, (CH
2) rCH
3, CN, OH, COOH, SO
3h, SO
3na, wherein, the integer that r is 1~30;
In formula IX, the integer that k, k ' they are 1~20; R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8can be the same or different, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8independently be selected from separately H, CH
3, (CH
2) rCH
3, CN, OH, COOH, SO
3h, SO
3na, two substituent positions that are labeled as on the phenyl ring of Mid are contraposition or a position; Wherein, the integer that r is 1~30;
In formula X, k, h, h ' can be the same or different, and k, h, h ' are independently selected from 1~20 integer separately; R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8can be the same or different, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8independently be selected from separately H, CH
3, (CH
2) rCH
3, CN,, OH, COOH, SO
3h, SO
3na, wherein, the integer that r is 1~30;
In formula XI, the integer that k is 1~20; R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10can be the same or different, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10independently be selected from separately H, CH
3, (CH
2) rCH
3, CN, OH, COOH, SO
3h, SO
3na, wherein, the integer that r is 1~30.
6. Polythioetherimide according to claim 1 and poly arylidene thio-ester alloy material, is characterized in that: described poly arylidene thio-ester has as shown in the formula the structural formula shown in I:
In formula I, the integer that d is 1~5000; R ' is selected from and replaces or unsubstituted aromatic group.
8. Polythioetherimide according to claim 1 and poly arylidene thio-ester alloy material, is characterized in that: described oxidation inhibitor is selected from one or more in hindered phenol antioxygen, phosphite antioxidant, sulfur-bearing oxidation inhibitor and metallic ion passivation agent;
Other described auxiliary agent comprises one or more in processing aid, thermo-stabilizer, lubricant, photostabilizer or ultraviolet absorbers.
9. according to the preparation method of the Polythioetherimide described in claim 1~8 any one and poly arylidene thio-ester alloy material, comprise the following steps:
(1) first by Polythioetherimide, poly arylidene thio-ester respectively at 130 ℃~180 ℃ vacuum-dryings;
(2) by dried Polythioetherimide and poly arylidene thio-ester, and oxidation inhibitor and other auxiliary agent be dry mixed in room temperature, after mixing, puts in twin screw extruder, by twin screw extruder extruding pelletization, makes Polythioetherimide and poly arylidene thio-ester alloy material;
In described twin screw extruder: district's temperature is 290 ℃~320 ℃; Two district's temperature are 320 ℃~340 ℃; Three district's temperature are 340 ℃~360 ℃; Four district's temperature are 350 ℃~380 ℃; Five district's temperature are 330 ℃~360 ℃; Six district's temperature are 320 ℃~340 ℃; Head temperature is 280 ℃~310 ℃; 300 revs/min~450 revs/min of engine speeds.
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US4455410A (en) * | 1982-03-18 | 1984-06-19 | General Electric Company | Polyetherimide-polysulfide blends |
CN1367192A (en) * | 2002-03-04 | 2002-09-04 | 中国科学院长春应用化学研究所 | Preparation method of dichlorophthalein imide and dichlorodiphenylketone or dichlorodiphenylsulfone copolymer |
CN101392055A (en) * | 2007-09-18 | 2009-03-25 | 中国科学院宁波材料技术与工程研究所 | Iso-poly(sulfide-imide) and preparation method thereof |
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Publication number | Priority date | Publication date | Assignee | Title |
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US4455410A (en) * | 1982-03-18 | 1984-06-19 | General Electric Company | Polyetherimide-polysulfide blends |
CN1367192A (en) * | 2002-03-04 | 2002-09-04 | 中国科学院长春应用化学研究所 | Preparation method of dichlorophthalein imide and dichlorodiphenylketone or dichlorodiphenylsulfone copolymer |
CN101392055A (en) * | 2007-09-18 | 2009-03-25 | 中国科学院宁波材料技术与工程研究所 | Iso-poly(sulfide-imide) and preparation method thereof |
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