CN102250469A - 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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- CN102250469A CN102250469A CN2010101777033A CN201010177703A CN102250469A CN 102250469 A CN102250469 A CN 102250469A CN 2010101777033 A CN2010101777033 A CN 2010101777033A CN 201010177703 A CN201010177703 A CN 201010177703A CN 102250469 A CN102250469 A CN 102250469A
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- 0 CN=CC=CC(S(*S(c1ccccc1)(=O)=O)(=O)=O)=C* Chemical compound CN=CC=CC(S(*S(c1ccccc1)(=O)=O)(=O)=O)=C* 0.000 description 1
- APNYHMZVKOTTBN-UHFFFAOYSA-N Cc(cc1)ccc1-c(cc1)ccc1S(c(cc1)ccc1-c1ccc(C)cc1)(=O)=O Chemical compound Cc(cc1)ccc1-c(cc1)ccc1S(c(cc1)ccc1-c1ccc(C)cc1)(=O)=O APNYHMZVKOTTBN-UHFFFAOYSA-N 0.000 description 1
- WEAYCYAIVOIUMG-UHFFFAOYSA-N Cc(cc1)ccc1S(c1ccc(C)cc1)(=O)=O Chemical compound Cc(cc1)ccc1S(c1ccc(C)cc1)(=O)=O WEAYCYAIVOIUMG-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- B29C2948/9259—Angular 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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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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
The high-molecular polymer alloy material is meant the multicomponent system that is made of two or more macromolecular material, belongs to alloy material.Physics blend, the block copolymerization in the 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, the technology status and the development prospect of engineering plastics based polymer alloy, Shanghai chemical industry, 2003,02).
Polythioetherimide, because the thioether bond flexible unit is incorporated in the inflexible polyimide main chain, this base polymer is except having outstanding thermomechanical property, have also that solvability is good, melt viscosity is low and the characteristics 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 that disclosed multiple Polythioetherimide all has excellent comprehensive performances such as good heat resistance, toughness height, melt viscosity be low in 200910153055.5 the Chinese patent application, and cost is relatively low, has good application prospects in association areas such as resistant to elevated temperatures engineering plastics, film, sizing agent, enameled wire, porous plastics, fiber and advanced composite materials.
Compare with poly arylidene thio-ester, polyimide exist processing forming poor, not alkali corrosion resistance, shortcoming such as cost an arm and a leg; And poly arylidene thio-ester has excellent chemical resistance, is being insoluble to any solvent below 200 ℃ substantially, the good mechanical performance, and relatively low cost and good advantages such as moulding processability, but its fragility is big, poor toughness, resistance to impact shock are low.Owing on the molecular chain of polyimide and poly arylidene thio-ester a large amount of aromatic nucleus is arranged all, structural similarity makes them have consistency preferably, the processing temperature of polyimide and poly arylidene thio-ester is complementary simultaneously, all in processing more than 300 ℃, therefore by the poly arylidene thio-ester modified polyimide, improve its processing forming and reduce cost, caused that people pay close attention to greatly.For example, disclose a kind of polyetherimide/polyphenylene sulfide alloy material in the U.S. Pat 4455410 (application of General Electric company), mainly introduced the imido preparation method of polyphenylene sulfide modified polyether.Document " sign of polyphenylene sulfide, polysulfones and polyetherimide binary and tertiary blending system " (Polymer Engineering and Science, 1991,32 (2): 84-91) disclose the blended modifier of polyphenylene sulfide and polyetherimide, blend is incompatible system, and the tensile strength of blend descends with the increase of polyphenylene sulfide content.A kind of polyimide/polyphenylene sulfide alloy material is disclosed in the U.S. Pat 4017555, with fused polyimide not by carrying out modification with the blend of 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 relatively poor, and polyphenylene sulfide is more crisp, cause the mechanical property of polyimide to damage bigger, employed on the other hand polyimide raw material price is expensive, and the cost value of the polyimide/poly arylidene thio-ester alloy material of feasible preparation is higher.
Summary of the invention
The invention provides a kind of Polythioetherimide and poly arylidene thio-ester alloy material, it has the good heat endurance energy, has excellent mechanical property such as high-modulus, high strength, high impact 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.
A kind of Polythioetherimide and poly arylidene thio-ester alloy material, form by following raw materials by 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 the I:
Among the formula I, m and n represent the polymerization degree respectively, and n is 1～20000 integer; , desirable 10 to 10000 integer or more integer;
M is 0～20000 integer; Desirable 10 to 10000 integer or more integer; When m=0, be the Polythioetherimide of homopolymerization; When m＞0, be the Polythioetherimide of copolymerization;
The position of thioether bond on the phthalimide structural unit is the 3-position or the 4-position of phthalimide structural unit in the Polythioetherimide;
A for replace or unsubstituted aliphatic group, replacement or unsubstituted aryl 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
10The cycloaliphatic ring alkyl in a kind of or at least two kinds of groups that connect with the C-C key and form.Described aromatic base is selected from C
6～C
30Aromatic group, further preferred C
6～C
30The benzene series aromatic group.For example, can select for use
A kind of or at least two kinds of groups that connect with the C-C key and form in them.
Described fragrant sulfone structural unit has as shown in the formula the structural formula shown in structural formula shown in the structural formula shown in the II, the formula III or the formula IV:
Among formula II, formula III or the formula IV, substituting group M is H, SO
3Li, SO
3Na, SO
3K or SO
3H; Close the position of substituting group M and thioether bond is ortho position, a position or contraposition;
Among the formula IV, Z is selected from a kind of in the following group:
Wherein, R is selected from a kind of in the following group:
A or b are 1～6 integer.
Described aromatic ketone structural unit has as shown in the formula structural formula shown in the structural formula shown in the structural formula shown in the structural formula shown in the V, the formula VI, the structural formula shown in the formula VII, the formula VIII, the structural formula shown in the formula IX, the formula X or the structural formula shown in the formula XI:
Perhaps
Among the formula V, K is 1～20 integer; 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 H, CH separately
3, (CH
2) rCH
3, CN, OH, COOH, SO
3H, SO
3Na, wherein, r is 1～30 integer;
Among the formula VI, k, k ', h, h ' can be the same or different, and k, k ', h, h ' independently are 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 H, CH separately
3, (CH
2) rCH
3, CN, OH, COOH, SO
3H, SO
3Na, wherein, r is 1～30 integer;
Among the formula VII, k, k ', h, h ' can be the same or different, and k, k ', h, h ' independently are 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 H, CH separately
3, (CH
2) rCH
3, CN, OH, COOH, SO
3H, SO
3Na, wherein, r is 1～30 integer;
Among the formula VIII, k is 1～20 integer; 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 H, CH separately
3, (CH
2) rCH
3, CN, OH, COOH, SO
3H, SO
3Na, wherein, r is 1～30 integer;
Among the formula IX, k, k ' are 1～20 integer; 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 H, CH separately
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 a contraposition or a position; Wherein, r is 1～30 integer;
Among the formula X, k, h, h ' can be the same or different, and k, h, h ' independently are 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 H, CH separately
3, (CH
2) rCH
3, CN, OH, COOH, SO
3H, SO
3Na, wherein, r is 1～30 integer;
Among the formula XI, k is 1～20 integer; 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 H, CH separately
3, (CH
2) rCH
3, CN, OH, COOH, SO
3H, SO
3Na, wherein, r is 1～30 integer.Described poly arylidene thio-ester has as shown in the formula the structural formula shown in the i:
Among the formula i, d is 1～5000 integer, desirable 10 to 1000 integer or more integer; R ' is selected from and replaces or unsubstituted aryl group.
Described R ' is selected from a kind of in the following groups:
Perhaps
Described oxidation inhibitor is selected from Hinered phenols antioxidant, phosphite ester kind antioxidant, contain in sulfur type antioxidant and the metallic ion passivation agent one or more.
The composite antioxidant that described multiple oxidation inhibitor is formed can be selected the composite antioxidant of Hinered phenols antioxidant and phosphite ester kind antioxidant for use, as in the commercially available prod such as composite antioxidant 215, composite antioxidant 225, composite antioxidant 561, composite antioxidant 900 one or more.
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 for use.
Described phosphite ester kind antioxidant can be selected one or more in the commercially available prod such as oxidation inhibitor 168, oxidation inhibitor TNP, oxidation inhibitor 626, oxidation inhibitor 618 for use.
Described optional with in the commercially available prod such as anti-oxidant DLTP, oxidation inhibitor DLTDP, oxidation inhibitor DSTP, oxidation inhibitor DSTDP one or more of sulfur type antioxidant that contain.
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. for use.
Described other auxiliary agent comprises one or more in processing aid, thermo-stabilizer, lubricant, photostabilizer or the 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 for use.
Described lubricant can be selected commercially available prod such as pentaerythritol stearate PETS-3 or pentaerythritol stearate PETS-4 for use.
Described ultraviolet absorbers can be selected one or more in the commercially available prod such as UV-531, UV-326, UV-327 for use.
Described processing aid and thermo-stabilizer can be selected this area processing aid and thermo-stabilizer commonly used for use.
The preparation method of described Polythioetherimide and poly arylidene thio-ester alloy material may further comprise the steps:
(1) earlier with Polythioetherimide, poly arylidene thio-ester respectively at 130 ℃～180 ℃ vacuum-dryings (more than 5 hours);
(2) Polythioetherimide and poly arylidene thio-ester that drying is good, and oxidation inhibitor and other auxiliary agent do in room temperature and mix, and puts in the twin screw extruder after mixing, and by the twin screw extruder extruding pelletization, makes Polythioetherimide and poly arylidene thio-ester alloy material;
In the 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 rev/mins～450 rev/mins 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 the Polythioetherimide processing forming is relatively poor, alkali corrosion resistance, price be not than costliness and shortcoming such as the poly arylidene thio-ester impact resistance is relatively poor, elongation at break is lower.
2, Polythioetherimide of the present invention and poly arylidene thio-ester alloy material, have good heat endurance energy, high-modulus, high strength, high impact and outstanding excellent comprehensive performances 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 the non-notch resistance to impact shock can reach 60KJ/m
2～200KJ/m
2, the resistance rank reaches the UL94-V-0 rank, is 93 ℃ in temperature and flooded respectively 24 hours in 30% (mass percentage concentration) aqueous sodium hydroxide solution and water that 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 of Cai Yonging is Polythioetherimide cheaply, this alloy has more price advantage than its like product, the product price ratio is higher, can bring higher economic benefit and social benefit, good application prospects be arranged in association areas such as thermostability engineering plastic, film, porous plastics, fiber and advanced composite materials.
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 is used 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 is formed, Polythioetherimide is this laboratory self-control, and the preparation method is that CN101463132A, CN101392055A, CN101531758A, CN101704950A and application number are the preparation method of disclosed multiple Polythioetherimide in 200910153055.5 the Chinese patent application by publication number.
Choosing the Polythioetherimide of homopolymerization respectively, is 0.53dL/g 30 ℃ of logarithmic viscosity numbers of measuring in meta-cresol, and structural formula is suc as formula shown in (ii):
Contain the copolymerization thioether imide 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 contain aromatic ketone structure copolymerization thioether imide, 30 ℃ of limiting viscosities in meta-cresol are 0.55dL/g, 350 ℃ of melt viscosities are the 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 for use, 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, contain in sulfur type antioxidant and the metallic ion passivation agent one or more, Hinered phenols antioxidant such as Switzerland Ciba company antioxidant 1010,1076; Phosphite ester kind antioxidant such as Switzerland Ciba company oxidation inhibitor 168, TNP; Contain sulfur type antioxidant such as the DLTP of Switzerland Ciba company, DSTP; Metallic ion passivation agent such as the IrganoxMD-1024 of Switzerland Ciba company.
Other auxiliary agent comprises processing aid, thermo-stabilizer, photostabilizer, lubricant etc., pentaerythritol stearate PETS-3, the PETS-4 of lubricant such as Italian FACI company; Resistance amine photostabilizer such as Switzerland Ciba company 770,944; Ultraviolet absorbers such as Milan, Nanjing UV-531 of chemical industry company limited or UV-326.
Embodiment 1
4-chloro-benzoic anhydride 91.28 grams (0.5mol) that in the 1L of dried and clean there-necked flask, add, 500 milliliters of N, N-N,N-DIMETHYLACETAMIDE (DMAc), add 49.56 gram (0.25mol) 4 after the stirring and dissolving, 4 '-dichloro-base ditane (MDA), be heated to 80 ℃ of reactions 2 hours, be warmed up to 130 ℃ of reactions 16 hours again, concentrating under reduced pressure is to about 200 milliliters then, be poured in 3 premium on currency, filter white solid, filter cake is given a baby a bath on the third day after its birth time with distilled water, 120 ℃ of vacuum dryings get two chlorine monomer crude product 116 grams, yield 88%.Be used for next step polyreaction behind the crude product vacuum fusion.
Under the nitrogen atmosphere, in 500 milliliters of there-necked flasks of dried and clean, add 26.37 gram (0.05mol) above-mentioned pair of chlorine monomers, 2.30 gram (0.05mol) anhydrous lithium sulfide, 200 milliliters of N-N-methyl-2-2-pyrrolidone N-s (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 the 2L water and was stirred 12 hours, filter, filter cake was with 90% (concentration expressed in percentage by volume) ethanol extracting 24 hours, get faint yellow polyimide powder 21.0 grams behind 150 ℃ of vacuum dryings, 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 polythioether imide shown in (ii).
Embodiment 2
In the 250ml there-necked flask, add 5.29g (0.01mol) 4,4 '-two (4-chloro imide) phenyl ether, 2.87g (0.01mol) 4 ', the 4-dichloro diphenyl sulfone, 0.67g (0.021mol) sulphur, 5.67g (0.063) trioxymethylene, 1.68g sodium hydroxide, 0.25g calcium chloride, add 100mlN-methyl-2-pyrrolidone (mass percent is 8%) after the logical nitrogen deoxygenation three times, be heated to 150 ℃ of reactions after 5 hours, added behind the 0.11g chlorobenzene reheat to 180 ℃ reaction behind the cool to room temperature 3 hours, the reaction solution cool to room temperature is carried out aftertreatment.
Reaction solution poured in the methyl alcohol lentamente stirred 2 hours, filter the back and use water boil 1 hour, filter, filter cake is got up with 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 with resulting polymers 200 ℃ of bakings 48 hours in vacuum drying oven.
30 ℃ of limiting viscosities in meta-cresol of resulting polymers are 0.65dL/g, and 350 ℃ of melt viscosities are 4000Pas, and structural formula is suc as formula the copolymerization thioether imide shown in (iii).
Embodiment 3
In the 250ml there-necked flask, add 5.29g (0.01mol) 4,4 '-two (4-chloro imide) phenyl ether, 2.51g (0.01mol) 4 ' 4-, two chloro benzophenones, 0.67g (0.021mol) sulphur, 5.67g (0.063) trioxymethylene, 1.68g sodium hydroxide, 0.50g calcium chloride, add 100mlN-methyl-2-pyrrolidone (solid content: 8%) after the logical nitrogen deoxygenation three times, be heated to 150 ℃ of reactions after 5 hours, added behind the 0.11g chlorobenzene reheat to 180 ℃ reaction behind the cool to room temperature 3 hours, the reaction solution cool to room temperature is carried out aftertreatment.
Reaction solution poured in the methyl alcohol lentamente stirred 2 hours, filter the back and use water boil 1 hour, filter, with filter cake with filter paper packet, mixing solutions (volume ratio 1: 1) with ethanol and acetone extracted wherein extracting 24 hours in Soxhlet, then with resulting polymers in vacuum drying oven 200 ℃ the baking 48 hours.
30 ℃ of limiting viscosities in meta-cresol of resulting polymers are 0.55dL/g, and 350 ℃ of melt viscosities are 4000Pas, and structural formula is suc as formula the copolymerization thioether imide shown in (iv).
Embodiment 4:
Earlier the equal polythioether imide of the formula that embodiment 1 is made shown in (ii), polyphenylene sulfide respectively in vacuum drying oven in 130 ℃ of vacuum-dryings 5 hours.
With dried equal polythioether imide (ii), polyphenylene sulfide, antioxidant 1010, oxidation inhibitor 168 and resistance amine photostabilizer 944 (Switzerland Ciba companies) mix 3min under room temperature in mixing tank (50rmp), all polythioether imide weight percent (ii) is 74.25% in the mixture, the weight percent of polyphenylene sulfide is 24.75%, the weight percent of antioxidant 1010 is 0.3%, the weight percent of oxidation inhibitor 168 is 0.2%, and the weight percent of resistance amine photostabilizer 944 is 0.5%.Material behind the 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: 315 ℃ of district's temperature, 330 ℃ of two district's temperature, 345 ℃ of three district's temperature, 355 ℃ of four district's temperature, 350 ℃ of five district's temperature, 330 ℃ of six district's temperature, 315 ℃ of head temperatures, 300 rev/mins of engine speeds.
Embodiment 5:
Earlier the equal polythioether imide of the formula that embodiment 1 is made shown in (ii), polyphenylene sulfide respectively in vacuum drying oven in 160 ℃ of vacuum-dryings 4 hours.
With dried equal polythioether imide (ii), polyphenylene sulfide, antioxidant 1010, oxidation inhibitor 168, resistance amine photostabilizer 944 (Switzerland Ciba companies) and UV-531 (Milan, Nanjing chemical industry company limited) mix 3min under room temperature in mixing tank (50rmp), equal polythioether imide weight percent (ii) is 49.5% in the mixture, the weight percent of polyphenylene sulfide is 49.5%, the weight percent of antioxidant 1010 is 0.3%, the weight percent of oxidation inhibitor 168 is 0.2%, the weight percent of resistance amine photostabilizer 944 is 0.2%, and the weight percent of UV-531 is 0.3%.Material behind the 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: 310 ℃ of district's temperature, 315 ℃ of two district's temperature, 320 ℃ of three district's temperature, 330 ℃ of four district's temperature, 330 ℃ of five district's temperature, 320 ℃ of six district's temperature, 305 ℃ of head temperatures, 400 rev/mins of engine speeds.
Embodiment 6:
Earlier the equal polythioether imide of the formula that embodiment 1 is made shown in (ii), polyphenylene sulfide respectively in vacuum drying oven in 150 ℃ of vacuum-dryings 5 hours.
With dried equal polythioether imide (ii), polyphenylene sulfide, antioxidant 1010, oxidation inhibitor 168, resistance amine photostabilizer 944 (Switzerland Ciba companies) and UV-326 (Milan, Nanjing chemical industry company limited) mix 3min under room temperature in mixing tank (50rmp), equal polythioether imide weight percent (ii) is 24.75% in the mixture, the weight percent of polyphenylene sulfide is 74.25%, the weight percent of antioxidant 1010 is 0.3%, the weight percent of oxidation inhibitor 168 is 0.2%, the weight percent of resistance amine photostabilizer 944 is 0.2%, and the weight percent of UV-326 is 0.3%.Material behind the 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: 310 ℃ of district's temperature, 315 ℃ of two district's temperature, 320 ℃ of three district's temperature, 330 ℃ of four district's temperature, 330 ℃ of five district's temperature, 320 ℃ of six district's temperature, 305 ℃ of head temperatures, 450 rev/mins of engine speeds.
Embodiment 7:
Earlier the equal polythioether imide of the formula that embodiment 1 is made shown in (ii), polyphenylene sulfide respectively in vacuum drying oven in 140 ℃ of vacuum-dryings 5 hours.
With dried equal polythioether imide (ii), polyphenylene sulfide, antioxidant 1010, oxidation inhibitor 168 and UV-326 (Milan, Nanjing chemical industry company limited) mix 3min under room temperature in mixing tank (50rmp), all polythioether imide weight percent (ii) is 9.9% in the mixture, the weight percent of polyphenylene sulfide is 89.1%, the weight percent of antioxidant 1010 is 0.3%, the weight percent of oxidation inhibitor 168 is 0.2%, and the weight percent of UV-326 is 0.5%.Material behind the 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: 310 ℃ of district's temperature, 315 ℃ of two district's temperature, 320 ℃ of three district's temperature, 330 ℃ of four district's temperature, 330 ℃ of five district's temperature, 320 ℃ of six district's temperature, 305 ℃ of head temperatures, 400 rev/mins of engine speeds.
Embodiment 8:
Earlier the copolymerization thioether imide that contain sulfone structure of the formula that embodiment 2 is made shown in (iii), polyphenylene sulfide respectively in vacuum drying oven in 150 ℃ of vacuum-dryings 5 hours.
With dried copolymerization thioether imide (iii), polyphenylene sulfide, antioxidant 1010, oxidation inhibitor 168, pentaerythritol stearate PETS-3 (Italian FACI company) and UV-326 (Milan, Nanjing chemical industry company limited) mix 3min under room temperature in mixing tank (50rmp), copolymerization thioether imide weight percent (iii) is 24.75% in the mixture, the weight percent of polyphenylene sulfide is 74.25%, the weight percent of antioxidant 1010 is 0.3%, the weight percent of oxidation inhibitor 168 is 0.2%, the weight percent of pentaerythritol stearate PETS-3 is 0.1%, and the weight percent of UV-326 is 0.4%.Material behind the 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: 310 ℃ of district's temperature, 315 ℃ of two district's temperature, 320 ℃ of three district's temperature, 330 ℃ of four district's temperature, 330 ℃ of five district's temperature, 320 ℃ of six district's temperature, 305 ℃ of head temperatures, 350 rev/mins of engine speeds.
Embodiment 9:
Earlier the copolymerization thioether imide that contain ketone structure of the formula that embodiment 3 is made shown in (iv), polyphenylene sulfide respectively in vacuum drying oven in 150 ℃ of vacuum-dryings 5 hours.
With dried copolymerization thioether imide (iv), polyphenylene sulfide, antioxidant 1010, oxidation inhibitor 168, pentaerythritol stearate PETS-3 (Italian FACI company) and UV-326 (Milan, Nanjing chemical industry company limited) (50rmp) in mixing tank mix 3min under room temperature, copolymerization thioether imide weight percent (iv) is 74.25% in the mixture, the weight percent of polyphenylene sulfide is 24.75%, the weight percent of antioxidant 1010 is 0.3%, the weight percent of oxidation inhibitor 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 behind the 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: 310 ℃ of district's temperature, 315 ℃ of two district's temperature, 320 ℃ of three district's temperature, 330 ℃ of four district's temperature, 330 ℃ of five district's temperature, 320 ℃ of six district's temperature, 305 ℃ of head temperatures, 350 rev/mins of engine speeds.
Comparative Examples 1:
Earlier the equal polythioether imide of the formula that embodiment 1 is made shown in (ii) in vacuum drying oven in 130 ℃ of vacuum-dryings 5 hours.
With dried equal polythioether imide (ii), antioxidant 1010, oxidation inhibitor 168 and resistance amine photostabilizer 770 (Switzerland Ciba companies) mix 5min under room temperature in mixing tank (50rmp), all polythioether imide weight percent (ii) is 99% in the mixture, the weight percent of antioxidant 1010 is 0.3%, the weight percent of oxidation inhibitor 168 is 0.2%, and the weight percent of resistance amine photostabilizer 770 is 0.5%.Material behind the mixing is joined in the hopper of twin screw extruder, through melt blending, extruding pelletization makes the Polythioetherimide material.
Wherein the processing conditions of twin screw extruder is: 315 ℃ of district's temperature, 330 ℃ of two district's temperature, 345 ℃ of three district's temperature, 355 ℃ of four district's temperature, 350 ℃ of five district's temperature, 330 ℃ of six district's temperature, 310 ℃ of head temperatures, 300 rev/mins of engine speeds.
Comparative Examples 2
Earlier the copolymerization thioether imide that contain sulfone structure of the formula that embodiment 2 is made shown in (iii) (iii) in vacuum drying oven in 130 ℃ of vacuum-dryings 5 hours.
With dried copolymerization thioether imide (iii), antioxidant 1010, oxidation inhibitor 168 and resistance amine photostabilizer 770 (Switzerland Ciba companies) mix 5min under room temperature in mixing tank (50rmp), copolymerization thioether imide weight percent (iii) is 99% in the mixture, the weight percent of antioxidant 1010 is 0.3%, the weight percent of oxidation inhibitor 168 is 0.2%, and the weight percent of resistance amine photostabilizer 770 is 0.5%.Material behind the mixing is joined in the hopper of twin screw extruder, through melt blending, extruding pelletization makes the Polythioetherimide material.
Wherein the processing conditions of twin screw extruder is: 315 ℃ of district's temperature, 330 ℃ of two district's temperature, 345 ℃ of three district's temperature, 355 ℃ of four district's temperature, 350 ℃ of five district's temperature, 330 ℃ of six district's temperature, 310 ℃ of head temperatures, 300 rev/mins of engine speeds.
Comparative Examples 3
Earlier the copolymerization thioether imide that contain ketone structure of the formula that embodiment 3 is made shown in (iv) (iv) in vacuum drying oven in 130 ℃ of vacuum-dryings 5 hours.
With dried copolymerization thioether imide (iv), antioxidant 1010, oxidation inhibitor 168 and resistance amine photostabilizer 770 (Switzerland Ciba companies) mix 5min under room temperature in mixing tank (50rmp), copolymerization thioether imide weight percent (iii) is 99% in the mixture, the weight percent of antioxidant 1010 is 0.3%, the weight percent of oxidation inhibitor 168 is 0.2%, and the weight percent of resistance amine photostabilizer 770 is 0.5%.Material behind the mixing is joined in the hopper of twin screw extruder, through melt blending, extruding pelletization makes the Polythioetherimide material.
Wherein the processing conditions of twin screw extruder is: 315 ℃ of district's temperature, 330 ℃ of two district's temperature, 345 ℃ of three district's temperature, 355 ℃ of four district's temperature, 350 ℃ of five district's temperature, 330 ℃ of six district's temperature, 310 ℃ of head temperatures, 300 rev/mins of engine speeds.
In order to characterize the fluidity of molten of Polythioetherimide and polyphenylene sulfide alloy, in BrabenderPlasticorder Mixer instrument, carry out torque-proportion relation test.
With equal polythioether imide (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 2h respectively, the material of mixing joined carry out melt blending in the Brabender torque rheometer, wherein the test conditions of melt blending is: blending temperature is 330 ℃, rotor speed is 30 rev/mins, reach balance until moment of torsion, test period is about 15 minutes, measure the torque rheology of Polythioetherimide and polyphenylene sulfide alloy, test result sees Table 1:
Table 1 Polythioetherimide/torque of polyphenylene sulfide alloy and proportion relation
| Equal polythioether imide/polyphenylene sulfide | Torque (N.m) | Polythioetherimide/polyphenylene sulfide | Torque (N.m) |
[0128]?
| 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 the torque reduction means that then 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 promptly its melt viscosity significantly reduces.Pure relatively Polythioetherimide, polyphenylene sulfide content are respectively 20% and at 30% o'clock, and torque has reduced by 27.7% and 54.0% respectively.So bright from torque rheology table with test results, can significantly reduce the melt viscosity of Polythioetherimide by adding polyphenylene sulfide, thereby improve its moulding processability significantly.
The alloy material that the foregoing description 1～6 is prepared, and Comparative Examples 1～3 prepared material 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 the 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 are 20mm/min.
The 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).
The heat-drawn wire performance detects according to GB GB 1634-79.Specimen size (mm): (80 ± 2) * (10 ± 0.2) * (4 soil 0.2).
The 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 is formed | Comparative Examples 1 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 |
| Equal polythioether imide (%) | 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 |
[0138]?
| 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 was matrix, the alloy material mechanical property was than the not too big variation of pure Polythioetherimide.But, when the content of polyphenylene sulfide surpasses 50% in alloy material, the mechanical property of alloy has descended much with respect to pure Polythioetherimide, this is because the mechanical property of alloy material is mainly reflected on the matrix, therefore when polyphenylene sulfide is matrix, mechanical property, especially impact strength decreased a lot.
Table 3
| Weight percent is formed | Comparative Examples 2 | Embodiment 8 | Comparative Examples 3 | Embodiment 9 |
| The copolymerization thioether imide (%) that contains the sulfone structure | 99 | 74.25 | 0 | 0 |
| The copolymerization thioether imines (%) that contains the 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 |
[0142]?
| 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 |
Can draw from the result of table 1, table 2 and table 3, adopt polyphenylene sulfide blended modified polysulfide ether imide, high temperature resistant and the excellent mechanical property that has not only kept Polythioetherimide is improved its processing forming thereby can also reduce its melt viscosity significantly.Simultaneously, because the polyimide that adopts is Polythioetherimide cheaply in this alloy, have more competitive power so this alloy is compared its like product on price, cost performance of product is higher.The Polythioetherimide and the polyphenylene sulfide alloy of the present invention preparation have the excellent comprehensive performance, can well serve fields such as aerospace, microelectronics, automobile, electric, new forms of energy.
Claims (10)
1. Polythioetherimide and poly arylidene thio-ester alloy material, make by following raw materials by weight percent:
Polythioetherimide 8%～95%;
Poly arylidene thio-ester 4%～90%;
Oxidation inhibitor 0.01%～1%;
Other auxiliary agent 0.01%～1%.
2. Polythioetherimide according to claim 1 and poly arylidene thio-ester alloy material is characterized in that: described Polythioetherimide has as shown in the formula the structural formula shown in the I:
Among the formula I, m and n represent the polymerization degree respectively, and n is 1～20000 integer; M is 0～20000 integer;
The position of thioether bond on the phthalimide structural unit is the 3-position or the 4-position of phthalimide structural unit in the Polythioetherimide;
A for replace or unsubstituted aliphatic group, replacement or unsubstituted aryl group in a kind of;
X is fragrant sulfone structural unit or aromatic ketone structural unit.
3. Polythioetherimide according to claim 2 and poly arylidene thio-ester alloy material is characterized in that: described aliphatic group is selected from C
1～C
10Aliphatic chain alkyl or C
3～C
10The cycloaliphatic ring alkyl in a kind of or at least two kinds of groups that connect with the C-C key and form;
Described aromatic base is selected from C
6～C
30Aromatic group.
4. Polythioetherimide according to claim 3 and poly arylidene thio-ester alloy material is characterized in that: described A is for being selected from
A kind of or at least two kinds of groups that connect with the C-C key and form in them.
5. 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 structural formula shown in the structural formula shown in the II, the formula III or the formula IV:
Among formula II, formula III or the formula IV, substituting group M is H, SO
3Li, SO
3Na, SO
3K or SO
3H; Close the position of substituting group M and thioether bond is ortho position, a position or contraposition;
Among the formula IV, Z is selected from a kind of in the following group:
Wherein, R is selected from a kind of in the following group:
A or b are 1～6 integer.
6. 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 structural formula shown in the structural formula shown in the structural formula shown in the structural formula shown in the V, the formula VI, the structural formula shown in the formula VII, the formula VIII, the structural formula shown in the formula IX, the formula X or the structural formula shown in the formula XI:
Perhaps
Among the formula V, K is 1～20 integer; 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 H, CH separately
3, (CH
2) rCH
3, CN, OH, COOH, SO
3H, SO
3Na wherein, r is 1～30 integer;
Among the formula VI, k, k ', h, h ' can be the same or different, and k, k ', h, h ' independently are 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 H, CH separately
3, (CH
2) rCH
3, CN, OH, COOH, SO
3H, SO
3Na, wherein, r is 1～30 integer.
Among the formula VII, k, k ', h, h ' can be the same or different, and k, k ', h, h ' independently are 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 H, CH separately
3, (CH
2) rCH
3, CN, OH, COOH, SO
3H, SO
3Na, wherein, r is 1～30 integer.
Among the formula VIII, k is 1～20 integer; 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 H, CH separately
3, (CH
2) rCH
3, CN, OH, COOH, SO
3H, SO
3Na, wherein, r is 1～30 integer;
In the formula IX, k, k ' are 1～20 integer; 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 H, CH separately
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 a contraposition or a position; Wherein, r is 1～30 integer.
Among the formula X, k, h, h ' can be the same or different, and k, h, h ' independently are 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 H, CH separately
3, (CH
2) rCH
3, CN,, OH, COOH, SO
3H, SO
3Na, wherein, r is 1～30 integer.
Among the formula XI, k is 1～20 integer; 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 H, CH separately
3, (CH
2) rCH
3, CN, OH, COOH, SO
3H, SO
3Na, wherein, r is 1～30 integer.
7. 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 the i:
Among the formula i, d is 1～5000 integer; R ' is selected from and replaces or unsubstituted aryl group.
8. Polythioetherimide according to claim 7 and poly arylidene thio-ester alloy material is characterized in that: described R ' is selected from a kind of in the following groups:
Perhaps
9. 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 the metallic ion passivation agent;
Described other auxiliary agent comprises one or more in processing aid, thermo-stabilizer, lubricant, photostabilizer or the ultraviolet absorbers.
10. according to the preparation method of each described Polythioetherimide of claim 1～9 and poly arylidene thio-ester alloy material, may further comprise the steps:
(1) earlier with Polythioetherimide, poly arylidene thio-ester respectively at 130 ℃～180 ℃ vacuum-dryings;
(2) Polythioetherimide and poly arylidene thio-ester that drying is good, and oxidation inhibitor and other auxiliary agent do in room temperature and mix, and puts in the twin screw extruder after mixing, and by the twin screw extruder extruding pelletization, makes Polythioetherimide and poly arylidene thio-ester alloy material;
In the 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 rev/mins～450 rev/mins of engine speeds.
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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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109705576A (en) * | 2018-12-27 | 2019-05-03 | 中广核高新核材科技（苏州）有限公司 | A kind of wear-resistant self-lubricating thermoplastic polyimide composite material and preparation method thereof |
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