CN106433125B - A kind of high-performance thermoplastic polyimides PP Pipe Compound and its manufacturing method - Google Patents
A kind of high-performance thermoplastic polyimides PP Pipe Compound and its manufacturing method Download PDFInfo
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- CN106433125B CN106433125B CN201610793928.9A CN201610793928A CN106433125B CN 106433125 B CN106433125 B CN 106433125B CN 201610793928 A CN201610793928 A CN 201610793928A CN 106433125 B CN106433125 B CN 106433125B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/12—Polymer mixtures characterised by other features containing additives being liquid crystalline or anisotropic in the melt
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Abstract
The present invention relates to a kind of manufacturing methods of thermotropic liquor polyester imide (LCPI) In-sltu reinforcement thermoplastic polyimide (TPI) PP Pipe Compound.The present invention relates to a kind of LCPI with TPI resin with excellent compatibility, it is compound using melt blending or " solution combined & molten alloy " is by the way of both in-situ blendings are compound, LCPI is set both to be used as the melt visbreaking agent of macromolecule TPI, it is used as in-situ fibrillation reinforcing agent again, improves melt-processable, dimensional stability and mechanical property of TPI resin etc..The invention avoids current liquid crystalline resins to enhance the deficiency that modified TPI technology needs additional expanding material or needs to be modified modified material, and simple process is easy and low in cost.In the present invention, processing fluidity, thermal property and the mechanical property etc. of thermoplastic polyimide can while significantly be improved by directly adding a small amount of LCPI (additive amount is within 5%).
Description
Technical field
The present invention relates to the blending and modifyings of composite material, more particularly to a kind of " solvable fusible " thermoplastic polyimide and heat
In-situ reaction, the alloying for causing liquid crystal polyester imide, prepare the technology of high-performance TPI PP Pipe Compound.
Background technique
Polyimides glue film is the relatively early heterocyclic polymer matrix resin for being applied to high-temperature Resistance Adhesives, with excellent resistance to
Hot and film forming can be divided into Thermocurable polyimide glue film and thermoplastic polyimide glue film two major classes.Thermoplasticity polyamides is sub-
Amine glue film has good film forming and flexibility, can be used for the bonding of large area and does not generate bubble, makes it in aerospace
And the fields such as microelectronics industry are used widely.
However, thermoplastic polyimide glue film (TPI) PP Pipe Compound requires lower melt viscosity, high-dimensional stability
With extremely low hygroscopicity, this is contradicted with the mechanical property of glue film and peel strength again.How simultaneously improve above-mentioned performance have it is larger
Difficulty.Currently, being generally blended using liquid crystal polymer (TLCP) with thermoplastic polyimide, the high dimensionally stable of TLCP is utilized
Property, agent of low hygroscopicity, low viscosity and thermotropic liquid crystal at the performance of fibre enhancing, above-mentioned TPI glue film is solved in a manner of In-sltu reinforcement
Performance is difficult to the problem improved simultaneously.CN1112599 is using thermotropic liquid crystal polymer and Thermocurable polyimide melt blending, body
There are diameters in system less than 10 microns, the thermotropic liquid crystal polymer fiber that is orientated in certain direction, plays humidification.
CN101870815 is related to a kind of polyetherimide composite material, TLCP is introduced into the PEI system of fiberglass reinforced, utilization is thermotropic
The thinning rheological property of liquid crystal polymer Strong shear reduces the melt viscosity of composite material；And thermotropic liquid crystal polymer is in PEI
It is capable of forming microfibrillar structure in matrix, improves the strength of materials.
The principle of the above-mentioned in-situ modified TPI of TLCP is: during melt-processed, under shearing force, TLCP's is rigid
Property chain link aligns, and when polymer cools down, TLCP just forms the liquid crystal fine fibrilation of high strength and modulus, these fento ratios
Surface area is big, may be homogenously dispersed in polyimides, plays a part of to enhance skeleton；When material receives external force, fento, which rises, to be born
The effect of stress and stress transfer.Since reinforcing effect is obtained by the fiber being formed in situ under viscosity flow state, no
It will increase melt viscosity, also avoid the fracture of fiber, to play the role of enhancing modified TPI.
But the study found that in the melt blending of TLCP and TPI, since thermodynamically, rigid molecule and flexible molecule are difficult
To reach compatible, the fento dispersibility for forming thermotropic liquid crystal in compound system is poor, in the section observable of composite material
To obvious skin-core structure.Therefore in the outer masterpiece used time, fento can not play the role of effectively meeting with stresses and stress transfer, cause multiple
The mechanical property of condensation material is poor, it is difficult to achieve the purpose that enhance TPI.During liquid crystal composite material preparation, volume is needed
The outer a variety of expanding materials of addition, or TLCP or TPI are modified, lead to complex process and higher cost.CN101560294 is disclosed
A kind of melt blending material of compatible thermotropic liquid crystal polymer and Polythioetherimide, discovery thermotropic liquid crystal polymer with
There are good compatibilities between PEI matrix.However, this method can only also realize liquid crystal polymer and the melt blending of TPI, it is still
The compatibility that the two can not be further increased, can not more preferably improve the enhancing and comprehensive performance of composite material.
Summary of the invention
In order to solve the above-mentioned problems in the prior art, it is former that the invention discloses a kind of thermotropic liquor polyester imides
The high-performance thermoplastic polyimides PP Pipe Compound of position enhancing.Wherein, the polyesterimide structure is as shown in flowering structure 1.
Wherein, R1Are as follows:OrEquiconjugate aromatic ring.R2Are as follows: OrEqual flexible groups.n1For 1~100, n2It is 1~10.
The polyesterimide can be obtained using preparation method well known in the art, if Li Shengyu is " polyesterimide
In synthesis and technical study " (synthesis of polyesterimide and technical study [D], Li Shengyu, East China University of Science, the 4-11 pages,
2013) it discloses, the synthetic method of polyesterimide is broadly divided into:
(1) one-step method: trimellitic anhydride, dihydric alcohol and diamine are raw material, and one-step synthesis polyesterimide is (referring to the 5th
Page paragraph 1, Fig. 2 .1),
(2) ester-interchange method: first synthesizing imide diacid, then it is subjected to transesterification with diacetate esters, it is sub- to generate polyester acyl
Amine (referring to page 5 2.3.1.2, Fig. 2 .2),
And (3) two-step method (referring to page 6 2.3.2.3, Fig. 2 .3).Two-step method is first to synthesize the dihydric alcohol containing imide ring
Or binary acid, then it is subjected to polycondensation reaction with binary acid or dihydric alcohol, polyesterimide is made, hot imidization method (ginseng can be divided into
See 1-2 sections of inverse of page 6, Fig. 2 .4) and chemical imidization method (referring to 1-2 sections of inverse of page 7, Fig. 2 .5 and 2.6).
On the other hand, the synthesis of polyesterimide is broadly divided into two methods: first is that by the binary acid containing imine structure
It reacts with the dihydric alcohol containing imine structure and generates polyesterimide monomer, monomer autohemagglutination again；It second is direct synthesis containing Asia
The carboxylic acid of amine structure, then intermolecular polymerization occurs, generate polyesterimide.Further, it is also possible to gather referring in CN101560294
The imido preparation method of ester obtains polyesterimide of the invention.In a particular embodiment, polyester acyl is prepared using two-step method
Imines: in the reaction flask with nitrogen protection, blender and water segregator, 0.02mol diamine monomer is dissolved in 100ml DMAc
In 40ml toluene Mixed Solvent, to after completely dissolution, 0.04mol trimellitic anhydride is added, react 6 in 140~150 DEG C~
After 8h, 160~180 DEG C of 2~4h of reaction, drying is washed, is obtained containing imido diacid monomer.Resulting diacid monomer is added again
In the mixed liquor for entering 0.8molDMF, 1.04mol benzene sulfonyl chloride and 400ml pyridine, at 80 DEG C after stirring and dissolving, then slowly to
Two phenol solutions of equimolar amounts are wherein added dropwise, it is washed, dry after 70~90 DEG C of 2~4h of reaction, polyesterimide is made.
Thermoplastic polyimide is melt-processable and/or soluble thermoplastic polyimide resin, preferably oxygen ether type, ketone
Ether type or thioether-type polyimides.
In-sltu reinforcement PP Pipe Compound of the invention can be used following method and be made: by 0.1~0.5 part of LCPI powder and 9.5~
10 parts of TPI powder dry method premixs, then application claims equipped with accurate weightlessness through double screw extruder melt blending In-situ reaction, or directly
Double screw extruder that LCPI-TPI is made through melt blending with 9.5~10 parts of TPI powders in 0.1~0.5 part of LCPI powder is special
Materials.LCPI under the action of shear force, is formed the fento with good draw ratio and is dispersed in TPI, reached with this
The effect of LCPI enhancing TPI.
Alternatively, LCPI and TPI is formed blending resin with the homogeneous blending method of glue, then carry out melt blending original position again
It closes.Specifically, 1) 9.5~10 parts of thermoplastic polyimide resins are dissolved in 80~150 parts of solvents, thereto be added 0.1~
0.5 part of thermotropic liquor polyester imide resin stirs 1~5 hour, forms homogeneous glue；2) by the homogeneous glue in step 1)
Liquid is poured into 200~600 parts of poor solvents and is precipitated, and by washing, drying and other steps, blend composition is made；It 3) will be described in step 2)
Blend composition through melting extrusion etc., PP Pipe Compound is made in In-situ reaction.Wherein, solvent described in step 1) is N, N- dimethyl acyl
One of common polar solvent such as amine, N-Methyl pyrrolidone, dimethyl sulfoxide, metacresol or more than one mixing；
Poor solvent described in step 2) is one of the low poles or nonpolar solvent such as water, ethyl alcohol, acetone or more than one is mixed
It closes.
LCPI-TPI PP Pipe Compound of the invention is that can be used for electronic package material (such as non-gel flexible copper-clad plate), bonding use
The PP Pipe Compound of TPI glue film and high-strength high-low temperature resistant TPI composite material.
The hard and soft segment of LCPI strand of the present invention assigns the performance of its thermotropic liquid crystal, imide group makes it in molecule knot
There can be preferable compatibility on structure with TPI resin.Moreover it is possible to be blended in the homogeneous mode of glue with TPI, from molecular scale
It ensure that the compound of the two, further improve the compatibility of the two, to preferably improve the comprehensive performance of composite material, keep away
Additional expanding material is exempted from or has needed to be modified LCPI and TPI, simple process is easy and low in cost.In the present invention program, make heat
Liquid crystal polyester imide is caused not only to be used as the melt visbreaking agent of macromolecule TPI, but also as in-situ fibrillation reinforcing agent；Directly addition is a small amount of
LCPI (additive amount is within 5%) can significantly improve processing fluidity, thermal property and the mechanical property etc. of TPI simultaneously.
In specific embodiment, TPI mobile performance improves 1~5 times, and tensile strength improves 10~20%, and bending strength improves 5~25%,
Unnotched impact strength improves 0.2~1.2 times.
Specific embodiment
It, below will be to the technology in the embodiment of the present invention in order to make those skilled in the art more fully understand the present invention program
Scheme is clearly and completely described, it is clear that and the described embodiment is only a part of the embodiment of the present invention, rather than
Whole embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creative work premise
Under every other embodiment obtained, should fall within the scope of the present invention.
Embodiment 1:
Firstly, take 0.205g liquid crystal polyester imide Resin A (structural formula is as follows, wherein n be 1~100) superfine powder,
The superfine powder of 10.038g Polythioetherimide resin B (structural formula is as follows, and wherein n is 1~100) is made special through melt blending
Materials.The melt index (MFR) for testing Polythioetherimide resin B is 1.2, tensile strength 102MPa, and bending strength is
122MPa, unnotched impact strength 25KJ/m2.The MFR of compound resin after melt blending is improved to 1.9, and tensile strength mentions
A height of 105MPa, bending strength rise to 125MPa, and unnotched impact strength rises to 31KJ/m2。
Embodiment 2: firstly, 0.502g liquid crystal polyester imide Resin A is taken, the grinding of 10.021g Polythioetherimide resin B
After blending, PP Pipe Compound is made in melt blending.The MFR of compound resin after melt blending is improved to 3.8, and tensile strength rises to
112MPa, bending strength rise to 131MPa, and unnotched impact strength rises to 42KJ/m2。
Embodiment 3:
It takes 10.07g Polythioetherimide resin B to be dissolved in 100ml DMAc solvent, adds the liquid crystal polyester of 0.102g
Imide resin A, stirring 2h dissolve it sufficiently, form homogeneous phase solution.The mixed glue solution is sprayed in 300ml water and is precipitated
Superfines, filtering, constant pressure and dry obtains composite powder, then the composite powder can be obtained original position through melting extrusion
Compound PP Pipe Compound, its processing of re-test and mechanical property.The MFR of In-situ reaction material obtained is improved to 2.3 after glue is blended, and is drawn
Stretching intensity is 101MPa, and bending strength rises to 126MPa, and unnotched impact strength rises to 32KJ/m2。
Embodiment 4:
It takes 10.035g Polythioetherimide resin B to be dissolved in 100ml DMAc solvent, adds the liquid crystal polyester of 0.203g
Imide resin A, stirring 2h dissolve it sufficiently, form homogeneous phase solution.The mixed glue solution is sprayed in 300ml water and is precipitated
Superfines, constant pressure and dry obtains composite powder, then it is special can be obtained In-situ reaction through melting extrusion for the composite powder
Materials, its processing of re-test and mechanical property.The MFR of In-situ reaction material obtained is improved to 3.7 after glue is blended, tensile strength
106MPa is risen to, bending strength rises to 129MPa, and unnotched impact strength rises to 40KJ/m2。
Embodiment 5:
It takes 10.007g Polythioetherimide resin B to be dissolved in 100ml DMAc solvent, adds the liquid crystal polyester of 0.304g
Imide resin A, stirring 2h dissolve it sufficiently, form homogeneous phase solution, which is sprayed in 300ml water and is precipitated
Superfines, filtering, constant pressure and dry obtains composite powder, then the blended powder can be obtained In-situ reaction through melting extrusion
PP Pipe Compound, its processing of re-test and mechanical property.The MFR of In-situ reaction material obtained is improved to 6.8 after glue is blended, and is stretched strong
Degree rises to 118MPa, and bending strength rises to 138MPa, and unnotched impact strength rises to 48KJ/m2。
Embodiment 6:
It takes 10.048g Polythioetherimide resin B to be dissolved in 100ml DMAc solvent, adds the liquid crystal polyester of 0.405g
Imide resin A, stirring 2h dissolve it sufficiently, form homogeneous phase solution, which is sprayed in 300ml water and is precipitated
Superfines, filtering, constant pressure and dry obtains composite powder, then the blended powder can be obtained In-situ reaction through melting extrusion
PP Pipe Compound, its processing of re-test and mechanical property.The MFR of In-situ reaction material obtained is improved to 8.7 after glue is blended, and is stretched strong
Degree rises to 121MPa, and bending strength rises to 143MPa, and unnotched impact strength rises to 54KJ/m2。
Embodiment 7:
It takes 10.041g Polythioetherimide resin B to be dissolved in 100ml DMAc solvent, adds the liquid crystal polyester of 0.505g
Imide resin A, stirring 2h dissolve it sufficiently, form homogeneous phase solution, which is sprayed in 300ml water and is precipitated
Superfines, filtering, constant pressure and dry obtains composite powder, then the blended powder can be obtained In-situ reaction through melting extrusion
PP Pipe Compound, its processing of re-test and mechanical property.The MFR of In-situ reaction material obtained is improved to 10.05 after glue is blended, and is stretched
Intensity rises to 125MPa, and bending strength rises to 151MPa, and unnotched impact strength rises to 55KJ/m2。
Embodiment 8:
It takes 10.057g Polythioetherimide resin B to be dissolved in 100ml DMAc solvent, adds the liquid crystal polyester of 0.312g
Imide resin C (structural formula is as follows, and wherein n is 1~100), stirring 2h dissolves it sufficiently, forms homogeneous phase solution, this is mixed
It closes glue to be sprayed in 300ml water superfines is precipitated, filter, constant pressure and dry obtains composite powder, then by the blending powder
End can obtain In-situ reaction PP Pipe Compound, its processing of re-test and mechanical property through melting extrusion.Original position obtained after glue is blended
The MFR of compound material is improved to 2.9, and tensile strength rises to 111MPa, and bending strength rises to 128MPa, unnotched impact strength
Rise to 31KJ/m2。
The above, the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although referring to before
Stating embodiment, invention is explained in detail, those skilled in the art should understand that: it still can be to aforementioned
Technical solution documented by each embodiment is modified or equivalent replacement of some of the technical features；And these are repaired
Change or replaces, the range for technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution.
Claims (10)
1. a kind of thermoplastic polyimide PP Pipe Compound, including thermoplastic polyimide and thermotropic liquor polyester imide, the heat
It causes the structure of liquid crystal polyester imide as follows, keeps thermotropic liquor polyester imide total with thermoplastic polyimide solution
It is mixed, form homogeneous glue:
Wherein, n is 1~100.
2. thermoplastic polyimide PP Pipe Compound as described in claim 1, which is characterized in that the thermoplastic polyimide is can
Melt-processed and/or soluble thermoplastic polyimide resin.
3. thermoplastic polyimide PP Pipe Compound as claimed in claim 1 or 2, which is characterized in that the thermoplastic polyimide
For melt-processable and/or soluble oxygen ether type, ether ketone type or thioether-type polyimides.
4. the preparation method of thermoplastic polyimide PP Pipe Compound described in any claim, feature in a kind of claim 1-3
It is, 0.1~0.5 part of thermotropic liquor polyester imide and 9.5~10 parts of thermoplastic polyimide is multiple in situ through melt blending
It closes, thermoplastic polyimide PP Pipe Compound is made.
5. the preparation method of thermoplastic polyimide PP Pipe Compound described in any claim, feature in a kind of claim 1-3
It is, by thermotropic liquor polyester imide and thermoplastic polyimide first through solution blending, then remelted blending is formed in situ
At the thermoplastic polyimide PP Pipe Compound of fibre enhancing.
6. preparation method as claimed in claim 4, which is characterized in that the preparation method specifically includes:
By 0.1~0.5 part of thermotropic liquor polyester imide and 9.5~10 parts of thermoplastic polyimide through double screw extruder machinery
Melt blending In-situ reaction is granulated, and obtains thermotropic liquor polyester imide modified thermoplastic polyimides PP Pipe Compound.
7. preparation method as claimed in claim 5, which is characterized in that the preparation method specifically includes:
1) 9.5~10 parts of thermoplastic polyimide are dissolved in 80~150 parts of solvents, 0.1~0.5 part of thermotropic liquid is added thereto
Brilliant polyesterimide, stirring, forms homogeneous glue；
2) homogeneous glue described in step 1) is precipitated in 200~600 parts of poor solvent, by washing, drying steps, system
Obtain blend composition；
3) thermoplastic polyimide PP Pipe Compound is made through melt blending In-situ reaction in blend composition described in step 2).
8. preparation method as claimed in claim 7, wherein solvent described in step 1) is one of polar solvent or one kind
Above mixing；Poor solvent described in step 2) is one of low pole or nonpolar solvent or more than one is mixed
It closes.
9. preparation method as claimed in claim 8, wherein solvent described in step 1) is N, N- dimethylformamide class, N- first
One of base pyrrolidones, dimethyl sulfoxide or metacresol or more than one mixing；Poor solvent described in step 2) is
One of water, ethyl alcohol or acetone or more than one mixing.
10. a kind of purposes of thermoplastic polyimide PP Pipe Compound as described in claim 1, which is characterized in that the PP Pipe Compound is used for
Electronic package material, bonding TPI glue film or high-strength high-low temperature resistant TPI composite material.
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| JP7467330B2 (en) * | 2019-01-10 | 2024-04-15 | 積水化学工業株式会社 | Ester compound, resin composition, cured product, and build-up film |
| CN111040448A (en) * | 2019-12-16 | 2020-04-21 | 中广核高新核材科技（苏州）有限公司 | Thermoplastic polyimide cable material for nuclear power aviation |
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|---|---|---|---|---|
| CN101560294A (en) * | 2009-05-19 | 2009-10-21 | 中山大学 | Compatible thermotropic liquid crystal polymer and method and application thereof |
| CN101870815A (en) * | 2010-07-02 | 2010-10-27 | 深圳市科聚新材料有限公司 | Glass fibre reinforced polyetherimide composite material and preparation method thereof |
| CN103554497A (en) * | 2013-10-30 | 2014-02-05 | 宏威高新材料有限公司 | Method for preparing flame-retardant thermoplastic polyimide resin |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07207156A (en) * | 1994-01-19 | 1995-08-08 | Yamaha Corp | Polyetherimide resin composition |
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|---|---|---|---|---|
| CN101560294A (en) * | 2009-05-19 | 2009-10-21 | 中山大学 | Compatible thermotropic liquid crystal polymer and method and application thereof |
| CN101870815A (en) * | 2010-07-02 | 2010-10-27 | 深圳市科聚新材料有限公司 | Glass fibre reinforced polyetherimide composite material and preparation method thereof |
| CN103554497A (en) * | 2013-10-30 | 2014-02-05 | 宏威高新材料有限公司 | Method for preparing flame-retardant thermoplastic polyimide resin |
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