CN1089776C - Method of preparing composite polymer-inorganic matter material - Google Patents
Method of preparing composite polymer-inorganic matter material Download PDFInfo
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- CN1089776C CN1089776C CN99123231A CN99123231A CN1089776C CN 1089776 C CN1089776 C CN 1089776C CN 99123231 A CN99123231 A CN 99123231A CN 99123231 A CN99123231 A CN 99123231A CN 1089776 C CN1089776 C CN 1089776C
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- hour
- imidization
- powder
- inorganic matter
- composite polymer
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- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 title claims description 28
- 239000000843 powder Substances 0.000 claims abstract description 49
- 239000000178 monomer Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000004132 cross linking Methods 0.000 claims abstract description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 14
- 239000007822 coupling agent Substances 0.000 claims description 13
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 229910017083 AlN Inorganic materials 0.000 claims description 11
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 claims description 11
- 239000011159 matrix material Substances 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- -1 amido benzene Chemical compound 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims 4
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 23
- 239000011147 inorganic material Substances 0.000 abstract description 23
- 150000001875 compounds Chemical class 0.000 abstract description 14
- 229910003471 inorganic composite material Inorganic materials 0.000 abstract description 5
- 229920002521 macromolecule Polymers 0.000 abstract description 5
- 229920005575 poly(amic acid) Polymers 0.000 abstract description 3
- 238000007259 addition reaction Methods 0.000 abstract description 2
- 238000012719 thermal polymerization Methods 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 21
- 238000005303 weighing Methods 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 6
- 125000003368 amide group Chemical group 0.000 description 5
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000002861 polymer material Substances 0.000 description 4
- 150000003384 small molecules Chemical class 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The present invention discloses a method for preparing a macromolecule inorganic composite material. The method comprises the following steps: firstly, a polyamic acid prepolymer is formed by using a PMR type monomer in a prepolymerization reaction, and the polyamic acid prepolymer is processed through imidization to obtain an imidization prepolymer (imidization powder); secondly, inorganic materials can compound with the PMR type monomer or a prepolymer not processed by imidization or a prepolymer processed by imidization in each of the stages; finally, the macromolecule inorganic composite material in a cross linking network structure is moulded by an addition reaction thermal polymerization mechanism. Macromolecule and the inorganic materials are compounded in any proportions with the method, and the compound of macromolecule and the inorganic materials is uniform; the obtained composite material has no gap and air bubbles, and has good performance.
Description
The present invention relates to the preparation method of composite polymer-inorganic matter material.
The preparation of polymer and inorganic composite materials, great majority are by macromolecular material finished product and inorganic materials compound back preparation.Usually viscosity is big, mobile poor because of macromolecule melt (or solution), makes compound irregularly, and is difficult to realize the compound of inorganic materials at high proportion; The common toughness of polymer powder is better, and particle is bigger, also is difficult to inorganic materials compound evenly.Also the someone attempts mixing with inorganic materials with high polymer monomer, carries out high molecular polymerization, moulding then, makes polymer and inorganic composite materials.This method is compound easily evenly, but has small molecules to emit in high molecular polymerization or moulding usually, so the gentle bubble in space will be arranged in the matrix material, thereby influences performance of composites.
In view of above-mentioned, it is compound to the purpose of this invention is to provide a kind of polymer and inorganic materials arbitrary proportion can realized, and compound evenly, the method for preparing composite polymer-inorganic matter material of excellent property.
Preparation method's provided by the invention key is to adopt the PMR processing method, it promptly is the method for polyimide add-on type monomer reactant polymerization Polymerization of monomeric reactants technology, prepare composite polymer-inorganic matter material with the PMR processing method, comprise earlier and generate the polyamic acid performed polymer with PMR type monomer prepolymerization reaction, carry out imidization again and obtain imidization performed polymer (imidization powder), inorganic materials can above-mentioned each stage or with PMR type monomer or with imidization before performed polymer or compound with the performed polymer after the imidization, with addition reaction thermopolymerization mechanism, be shaped to crosslinked reticular polymer-inorganic composite materials at last.
PMR type monomer is the mixture of two amido benzene, tetracarboxylic acid benzene and END CAPPED GROUP, as adopt MDA (4,4 '-two amido ditanes), BTDE (3,3 '-4,4 '-benzophenone tetracarboxylic acid dimethyl ester) and NE (5-norbornylene-2,3-mono methyl dicarboxylate) by 3～3.5: 2～2.4: 2 mixed in molar ratio forms.
Inorganic material can be aluminium nitride or aluminum oxide or metal-powder or other inorganic powder.
For realizing the object of the invention, the technical scheme of taking has:
Scheme 1:
The method for preparing composite polymer-inorganic matter material may further comprise the steps: earlier with PMR type monomer and inorganic material powders uniform mixing, 120～150 ℃ of reactions 0.5～2 hour in the vacuum drying oven then must PMR type monomer and inorganic material powders performed polymer matrix material; Again in baking oven 180～210 ℃ and 230～250 ℃ reacted respectively 0.5～2 hour, make the matrix material imidization; Last 300～320 ℃, 0.25～4 hour, 10～400MPa are hot-forming, the composite polymer-inorganic matter material of crosslinking structure, form stable.
Scheme 2:
The method for preparing composite polymer-inorganic matter material may further comprise the steps: earlier with 120～150 ℃ of reactions 0.5～2 hour in vacuum drying oven of PMR type monomer, obtain PMR performed polymer powder; Then with the inorganic material powders uniform mixing, again in baking oven 180～210 ℃ and 230～250 ℃ reacted respectively 0.5～2 hour, PMR type monomer and inorganic material powders imidization matrix material; Last 300～320 ℃, 0.25～4 hour, 10～400MPa are hot-forming, the composite polymer-inorganic matter material of crosslinking structure, form stable.
Scheme 3:
The method for preparing composite polymer-inorganic matter material may further comprise the steps: earlier with 120～150 ℃ of reactions 0.5～2 hour in vacuum drying oven of PMR type monomer, make PMR type monomer become performed polymer, again in baking oven 180～210 ℃ and 230～250 ℃ reacted respectively 0.5～2 hour, obtain imidization PMR powder; Then with monomeric imidization powder of PMR type and inorganic material powders uniform mixing, last 300～320 ℃, 0.25～4 hour, 10～400MPa are hot-forming, the composite polymer-inorganic matter material of crosslinking structure, form stable.
Scheme 4:
The method for preparing composite polymer-inorganic matter material may further comprise the steps: earlier with 120～150 ℃ of reactions 0.5～2 hour in vacuum drying oven of PMR type monomer, make PMR type monomer become performed polymer, again in baking oven 180～210 ℃ and 230～250 ℃ reacted respectively 0.5～2 hour, obtain imidization PMR powder; The uniform mixing in the solution of coupling agent with inorganic material powders and coupling agent simultaneously, the place to go solvent obtains the uniform mixture of inorganic material powders and coupling agent.Then with the monomeric imidization powder of PMR type and inorganic material powders and coupling agent mixture uniform mixing, last 300～320 ℃, 0.25～4 hour, 10～400MPa are hot-forming, the composite polymer-inorganic matter material of crosslinking structure, form stable.Here, coupling agent can be silane coupling agent or titanate coupling agent, has used coupling agent, can optimize the interface of polymer and inorganic materials.
Such scheme 1 preparation method's monomer mixture is a low-viscosity (mobile) liquid solution, adopts monomer mixture to mix with inorganic powder, and is easy to process, mixes easily, and allows the inorganic materials of larger proportion to sneak into.Scheme 2,3,4 preparation methods adopt performed polymer powder or imidization powder to mix with inorganic powder, because of performed polymer powder and imidization powder all more crisp, inviscid, can obtain than fine powder, with inorganic materials uniform mixing easily, and mix by this powder, can realize the compound of polymer and inorganic materials arbitrary proportion.
Usually, the monomeric consumption of PMR type is 99～20 (weight %), and the consumption of inorganics is 1.0～80 (weight %), and the coupling agent consumption is 0～1.0 (weight %).
Below in conjunction with example in detail:
Example 1
Earlier with 4,4 '-two amido ditanes, 3,3 '-4,4 '-benzophenone tetracarboxylic acid dimethyl ester and 5-norbornylene-2, PMR type monomer weighing 80 (the weight %) that the 3-mono methyl dicarboxylate forms by 3.087: 2.087: 2 mixed in molar ratio and the alumina powder uniform mixing of weighing 20 (weight %), then in the vacuum drying oven 140 ℃ the reaction 2 hours, PMR type monomer and alumina powder performed polymer matrix material; Again in baking oven 200 ℃ and 245 ℃ reacted respectively 1 hour, make the matrix material imidization; Last 315 ℃, 1 hour, 180MPa are hot-forming, the composite polymer-inorganic matter material of crosslinking structure, form stable, its voidage＜1%.
Example 2
Earlier with 4,4 '-two amido ditanes, 3,3 '-4,4 '-benzophenone tetracarboxylic acid dimethyl ester and 5-norbornylene-2, the PMR type monomer that the 3-mono methyl dicarboxylate forms by 3.087: 2.087: 2 mixed in molar ratio 1400C reaction 1 hour in vacuum drying oven obtains PMR performed polymer powder; Accurate this powder of weighing 50 (weight %) then, with itself and the accurate aluminium nitride powder uniform mixing of weighing 50 (weight %), again in baking oven 200 ℃ and 245 ℃ reacted respectively 1 hour, must PMR type monomer and aluminium nitride powder imidization matrix material; Last 315 ℃, 1 hour, 180MPa are hot-forming, the composite polymer-inorganic matter material of crosslinking structure, form stable, its voidage＜1%.
Example 3
With 4,4 '-two amido ditanes, 3,3 '-4,4 '-benzophenone tetracarboxylic acid dimethyl ester and 5-norbornylene-2, the PMR type monomer that the 3-mono methyl dicarboxylate forms by 3.087: 2.087: 2 mixed in molar ratio 140 ℃ of reactions 1 hour in vacuum drying oven, again in baking oven 200 ℃ and 240 ℃ reacted respectively 2 hours and 1 hour, obtain imidization PMR powder, accurate this powder of weighing 20 (weight %), with its aluminium nitride powder uniform mixing with accurate weighing 80 (weight %), last 315 ℃, 1 hour, 180MPa is hot-forming, obtains crosslinking structure, the composite polymer-inorganic matter material of form stable, its voidage＜2%.
Example 4
With 4,4 '-two amido ditanes, 3,3 '-4,4 '-benzophenone tetracarboxylic acid dimethyl ester and 5-norbornylene-2, the PMR type monomer that the 3-mono methyl dicarboxylate forms by 3.087: 2.087: 2 mixed in molar ratio 140 ℃ of reactions 1 hour in vacuum drying oven, again in baking oven 200 ℃ and 240 ℃ reacted respectively 2 hours and 1 hour, obtain imidization PMR powder; The aluminium nitride powder of simultaneously accurate weighing 98 (weight %) is with its H with accurate weighing 2 (weight %)
2N (CH
2)
3Si (OC
2H
5)
3Coupling agent is uniform mixing in its solution, and the place to go solvent obtains the uniform mixture of aluminium nitride powder and coupling agent.Accurately the imidization powder of weighing 50 (weight %) and the aluminium nitride powder of accurately weighing 50 (weight %) and the mixture uniform mixing of coupling agent then, last 315 ℃, 1 hour, 180MPa are hot-forming, the composite polymer-inorganic matter material of crosslinking structure, form stable.Its voidage＜1%.
The present invention adopts PMR type monomer or performed polymer and inorganic materials compound, and is compound even; And the performed polymer after the imidization is a fragile powder, can realize compound with the inorganic powder arbitrary proportion; Because mixture viscosity is low before the forming materials, can fully discharge the small molecules of emitting in the pre-polymerization, does not have small molecules to emit in the forming materials process, thus tight and bubble in the matrix material, excellent property.
Claims (4)
1. the method for preparing composite polymer-inorganic matter material, it is characterized in that comprising the steps: earlier mixture and aluminium nitride or aluminum oxide or metal-powder uniform mixing with two amido benzene, tetracarboxylic acid benzene and end-capping reagent, then in the vacuum drying oven 120～150 ℃ reacted 0.5～2 hour; Again in baking oven 180～210 ℃ and 230～250 ℃ reacted respectively 0.5～2 hour, make the matrix material imidization; Last 300～320 ℃, 0.25～4 hour, 10～400MPa are hot-forming, the composite polymer-inorganic matter material of crosslinking structure, form stable.
2. the method for preparing composite polymer-inorganic matter material is characterized in that comprising the steps: earlier 120～150 ℃ of reactions 0.5～2 hour in vacuum drying oven of mixture with two amido benzene, tetracarboxylic acid benzene and end-capping reagent; Then with aluminium nitride or aluminum oxide or metal-powder uniform mixing, again in baking oven 180～210 ℃ and 230～250 ℃ reacted respectively 0.5～2 hour; Last 300～320 ℃, 0.25～4 hour, 10～400MPa are hot-forming, the composite polymer-inorganic matter material of crosslinking structure, form stable.
3. the method for preparing composite polymer-inorganic matter material is characterized in that comprising the steps:
Earlier with 120～150 ℃ of reactions 0.5～2 hour in vacuum drying oven of the mixture of two amido benzene, tetracarboxylic acid benzene and end-capping reagent; Again in baking oven 180～210 ℃ and 230～250 ℃ reacted respectively 0.5～2 hour, obtain the imidization powder; Then with gained with aluminium nitride or aluminum oxide or metal-powder uniform mixing, last 300～320 ℃, 0.25～4 hour, 10～400MPa are hot-forming, the composite polymer-inorganic matter material of crosslinking structure, form stable.
4. the method for preparing composite polymer-inorganic matter material is characterized in that comprising the steps: earlier 120～150 ℃ of reactions 0.5～2 hour in vacuum drying oven of mixture with two amido benzene, tetracarboxylic acid benzene and end-capping reagent; Again in baking oven 180～210 ℃ and 230～250 ℃ reacted respectively 0.5～2 hour, obtain imidization polyimide add-on type monomer reactant polymeric powder; Simultaneously with aluminium nitride or aluminum oxide or metal-powder and silane coupling agent or titanate coupling agent uniform mixing in the solution of coupling agent, remove solvent, thing is uniformly mixed, then with this mixture and above-mentioned imidization powder uniform mixing, last 300～320 ℃, 0.25～4 hour, 10～400MPa are hot-forming, the composite polymer-inorganic matter material of crosslinking structure, form stable.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99123231A CN1089776C (en) | 1999-11-05 | 1999-11-05 | Method of preparing composite polymer-inorganic matter material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99123231A CN1089776C (en) | 1999-11-05 | 1999-11-05 | Method of preparing composite polymer-inorganic matter material |
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| CN1295096A CN1295096A (en) | 2001-05-16 |
| CN1089776C true CN1089776C (en) | 2002-08-28 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104473042B (en) * | 2010-03-19 | 2018-03-13 | 日清食品控股株式会社 | Instant noodles and its manufacture method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01103665A (en) * | 1987-10-15 | 1989-04-20 | Calp Corp | Plating resin composition |
| JPH0260960A (en) * | 1988-08-29 | 1990-03-01 | Mitsubishi Gas Chem Co Inc | Molding process |
| JPH03138808A (en) * | 1989-10-23 | 1991-06-13 | Toshiba Chem Corp | Electrically conductive resin component material and its moldings |
| JPH03182557A (en) * | 1989-12-12 | 1991-08-08 | Toshiba Chem Corp | Metal fiber-reinforced resin composition and molded article thereof |
-
1999
- 1999-11-05 CN CN99123231A patent/CN1089776C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01103665A (en) * | 1987-10-15 | 1989-04-20 | Calp Corp | Plating resin composition |
| JPH0260960A (en) * | 1988-08-29 | 1990-03-01 | Mitsubishi Gas Chem Co Inc | Molding process |
| JPH03138808A (en) * | 1989-10-23 | 1991-06-13 | Toshiba Chem Corp | Electrically conductive resin component material and its moldings |
| JPH03182557A (en) * | 1989-12-12 | 1991-08-08 | Toshiba Chem Corp | Metal fiber-reinforced resin composition and molded article thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104473042B (en) * | 2010-03-19 | 2018-03-13 | 日清食品控股株式会社 | Instant noodles and its manufacture method |
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| CN1295096A (en) | 2001-05-16 |
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