CN105175739A - Preparation method of organic silicon and polyimide material - Google Patents
Preparation method of organic silicon and polyimide material Download PDFInfo
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- CN105175739A CN105175739A CN201510617626.1A CN201510617626A CN105175739A CN 105175739 A CN105175739 A CN 105175739A CN 201510617626 A CN201510617626 A CN 201510617626A CN 105175739 A CN105175739 A CN 105175739A
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Abstract
The invention provides a preparation method of an organic silicon and polyimide material. The preparation method includes the steps that firstly, multi-element aromatic acid anhydride and polyisocyanates are pre-polymerized under a certain condition, isocyanate group end capped polyimide is obtained, an intermediate and hydroxyl silicone oil react to introduce organic silicon chain segments into a molecular structure, and finally target matter is obtained through high-temperature treatment. The controllability of the content of the organic silicon molecular chain segments of the prepared organic silicon-polyimide material is high, the material has excellent heat resistance and water repellence, and meanwhile a resin matrix shows high flexibility and good solubility. Compared with a traditional preparation process of the material, the method is low in raw material cost, wide in selective range, simple in preparation process and moderate in reaction condition, the controllability of the content of organic silicon can be effectively improved, and thus early realization and wide application of the material in industrial production can be better facilitated.
Description
Technical field
That the present invention relates to is a kind of preparation method, particularly a kind of preparation method of organosilicon-polyimide material of macromolecular material.
Background technology
The performance advantage of organosilicon and polyimide material can effectively merge by organosilicon-polyimide material.Such material had both had resistant of high or low temperature specific to polyimide, chemical stability, flame retardant resistance, had again kindliness specific to organosilicon and organic solvent-soluble.Organosilicon-polyimide material effectively can solve bi-material performance deficiency separately again having the excellent physicochemical property of bi-material concurrently simultaneously, therefore obtains the extensive concern of researcher.
The people such as Changzhou in 2010 chemistry institute Zhang Baotan arrange and report the preparation method of current organosilicon-polyimide material in detail " engineering plastics application " is upper, wherein most study, the most effectively surely belong to segment copolymerization method.Segment copolymerization method not only can be made silicone segments be evenly distributed in organosilicon-polyimide material molecule segment but also effectively can be improved solvability and the workability of polyalcohol integral by the change of silicone segments molecular structure.The reaction type at present preparing organosilicon-polyimide material by segment copolymerization method mainly comprises following a few class: the acid anhydrides that V.H.Kuckertz etc. report at first and siliceous amine condensation reaction, this reaction type relies on the two-step approach technology of preparing of polyimide, is to prepare organosilicon-polyimide material most study, the most frequently used, the most ripe reaction type at present; The acid anhydrides that the people such as N.D.Ghatge reported in nineteen eighty-three and siliceous isocyanic ester copolyreaction, this reaction type relies on the single stage method technology of preparing of polyimide; The people such as LYaMoshinskii are in the addition reaction of silicon with hydrogen of report in 1969, and in this reaction type 4H-3,1-benzoxazine-2,4(1H)-dione, thiazolinyl realizes being polymerized with the addition reaction of si-h bond.Although aforesaid method all can successfully prepare organosilicon-polyimide material, all there is certain problem: condensation reaction type owing to relying on the two-step approach technology of preparing of polyimide, therefore preparation technology's more complicated; In copolyreaction type and addition reaction type, siliceous isocyanic ester, narrower containing the polynary acid anhydride of alkene, Silicon Containing Hydrogen wet goods monomeric species selectable range; Required siliceous amine, siliceous isocyanic ester and Silicon Containing Hydrogen wet goods starting material are not only expensive but also existing market supply is less, can not meet the needs that organosilicon-polyimide material is produced in enormous quantities, be therefore unfavorable for that the industrialization of such material and cost degradation are produced.Meanwhile, when preparing organosilicon-polyimide material by aforesaid method, want effectively to regulate when content of polysiloxane is to improve composite property in material and could can only be realized by the mode changing silicon-containing monomer kind.But not only kind is very limited to can be used for preparing the silicon-containing monomer of organosilicon-polyimide material at present, and expensive, therefore greatly reduce controllability and the feasibility of actually operating.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of technique is simple, segment content is controlled, the cost of material is low organosilicon and polyimide material.
The object of the present invention is achieved like this:
The massfraction of material chemical constitution is: polynary fragrant acid anhydride 10 ~ 30 parts, intensive polar solvent 50 ~ 300 parts, polyisocyanates 10 ~ 25 parts, weak polar solvent 10 ~ 60 parts, hydroxy silicon oil 0 ~ 25 part, catalyzer 0.5 ~ 2 part, and preparation process comprises:
(1) polynary fragrant acid anhydride and polyisocyanates react and prepare isocyanate-terminated polyimide
The intensive polar solvent solution of polynary fragrant acid anhydride and the weak polar solvent solution of polyisocyanates is prepared under room temperature, the weak polar solvent solution of polyisocyanates is joined in container, under nitrogen protection, the oil bath heating of 35 ~ 50 DEG C, pressure is added polynary fragrant acid anhydride intensive polar solvent solution after solution temperature is constant, after generating without gas to solution, stop heating obtaining isocyanate-terminated polyimide solution;
(2) synthesis of organosilicon-polyimide material
Hydroxy silicon oil and catalyst mixed liquid are added drop-wise under room temperature in the product that step (1) obtains, react and obtain organosilicon-polyimide material solution after 2 ~ 4 hours, dry 2 ~ 4 hours of the air dry oven being placed in 200 ~ 240 DEG C obtains organosilicon-polyimide material except desolventizing.
The present invention can also comprise:
1, the described dropping VDE rate of addition in step (1) and step (2) controls to be 1 ~ 3ml/min.
2, described polynary fragrant acid anhydride is pyromellitic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-xenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-oxydiphthalic, 3,3 ', 4,4 '-xenyl sulfone tetracarboxylic dianhydride, mellitic acid three acid anhydride, three trimellitic acid 1,2-anhydride-1,3,5-benzene three esters or 1, one in 3,5-tri-oxygen-three (4-phthalic anhydride) benzene or mixture.
3, described intensive polar solvent is N-Methyl pyrrolidone, DMF, N,N-dimethylacetamide or dimethyl sulfoxide (DMSO); Described weak polar solvent is benzene, toluene or dimethylbenzene.
4, described polyisocyanates is diphenylmethanediisocyanate (MDI), tolylene diisocyanate (TDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) or polyphenyl polymethylene polyisocyanates (PAPI).
5, described catalyzer is one in stannous octoate, dibutyl tin laurate or Di-n-Butyl Amine or mixture.
6, described hydroxy silicon oil is one in polydimethylsiloxane type hydroxy silicon oil, polyphenyl methyl siloxane type hydroxy silicon oil or mixture; Hydroxyl Content in Hydroxysilicone fluid is 6.0 ~ 12.0%.
7, contained by acid anhydride base amount of substance contained by described polynary fragrant acid anhydride and hydroxy silicon oil, the amount sum of hydroxylated material equals isocyanate group amount of substance contained by polyisocyanates, and the ratio of hydroxyl and acid anhydride base amount of substance is between 0.0:1.0 ~ 0.4:0.6.
For effectively simplifying organosilicon-polyimide material preparation technology, realizing the controllability of different segment content, reducing material price, accelerate the pace of progress of organosilicon-polyimide material suitability for industrialized production, the one-step preparation process of polyimide and hydroxyl silicon oil modified urethane preparation technology combine by the present invention, provide novel method prepared by a kind of organosilicon-polyimide material.Present method first according to pre-designed polyimide and content of polysiloxane by the polynary aromatic anhydride of corresponding proportioning and polyisocyanates pre-polymerization under certain condition, obtain isocyanate-terminated polyimide, reacting with intermediate and hydroxy silicon oil is incorporated in molecular structure by silicone segments again, obtains target substance finally by pyroprocessing.Prepared organosilicon-polyimide material shows excellent thermotolerance, hydrophobic performance, higher snappiness and good solvability.Compared with the conventional preparation techniques of such material, the method raw materials is with low cost and selectable range is wider, effectively can reduce product price; Preparation flow is simple, reaction conditions temperature, greatly can simplify the preparation technology of organosilicon-polyimide material; Synthetic route is novel, belongs to the new approaches that is prepared organosilicon-polyimide material, can facilitate, effectively improves the controllability of organosilicon and polyimide content in material.Therefore the method is advantageously in realization early and the widespread use of organosilicon-polyimide material suitability for industrialized production, reaches the object of invention.
Compared with prior art, the present invention is owing to being incorporated into the preparation flow of organosilicon-polyimide material simultaneously by the one-step preparation process of polyimide and hydroxyl silicon oil modified urethane preparation technology, not only effectively simplify technical process prepared by material, and the relative content of organosilicon and polyimide segment can rely on merely this simple method of extent of polymerization changing hydroxy silicon oil to carry out Effective Regulation in material, and do not need by selecting the mode of novel hydroxyl silicone oil to realize, substantially increase feasibility and the controllability of experimental implementation.Meanwhile, the market value of hydroxy silicon oil is well below siliceous diamines, siliceous isocyanic ester, containing hydrogen silicone oil, and therefore the appearance of this kind of method will reduce the preparation cost of material greatly.Simple technology of preparing and the cheap prices of raw and semifnished materials will promote organosilicon-polyimide material suitability for industrialized production and greatly at the industry-wide pace of progress of its people.
Embodiment
By the following examples the present invention is described in further detail, and unrestricted scope involved in the present invention.
Embodiment 1
In 250ml there-necked flask, add 21.3gPAPI and 40g toluene and add magneton unlatching magnetic stirring apparatus and stir, connect reflux condensing tube and nitrogen protection device subsequently, the oil bath pan being placed in 45 DEG C heats.
Take pyromellitic acid dianhydride 12.2g and be dissolved in 100gN, N-N,N-DIMETHYLACETAMIDE, be added drop-wise in there-necked flask with the speed of 3ml/min with the N,N-dimethylacetamide solution of constant pressure funnel by pyromellitic acid dianhydride.To there-necked flask, solution no longer includes after gas produces and stops heating, obtains the isocyanate-terminated polyimide solution of red-brown clear, is cooled to room temperature set aside for use.
Take polydimethylsiloxane type hydroxy silicon oil 8.2g that 1g gram of dibutyl tin laurate and hydroxy radical content are 10% to mix and be placed in constant pressure funnel, be added drop-wise in there-necked flask with the speed of 2ml/min, react at ambient temperature with isocyanate-terminated polyimide, react and obtain organosilicon-polyimide material solution after 3 hours.Air dry oven solution being placed in 240 DEG C removes organosilicon-polyimide material that desolventizing obtains yellow for dry 6 hours.
Obtained organosilicon-polyimide material content of polysiloxane is 22.3%, polyimide segment content is 60.3%, amide functional mass contg 5.5%, initial decomposition temperature is higher than 280 DEG C, 5% mass loss temperature is more than 320 DEG C, contact angle reaches 100 °, in strong polar organic solvent, show good solvability.
Embodiment 2
In 250ml there-necked flask, add 16.0gPAPI and 30g m-xylene and add magneton unlatching magnetic stirring apparatus and stir, connect reflux condensing tube and nitrogen protection device subsequently, the oil bath pan being placed in 45 DEG C heats.
Take 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride 11.5g is dissolved in 120gN, N-N,N-DIMETHYLACETAMIDE, is added drop-wise in there-necked flask with the speed of 3ml/min with the N,N-dimethylacetamide solution of constant pressure funnel by pyromellitic acid dianhydride.To there-necked flask, solution no longer includes after gas produces and stops heating, obtains the isocyanate-terminated polyimide solution of red-brown clear, is cooled to room temperature set aside for use.
Take polydimethylsiloxane type hydroxy silicon oil 8.2g that 1g gram of dibutyl tin laurate and hydroxy radical content are 10% to mix and be placed in constant pressure funnel, be added drop-wise in there-necked flask with the speed of 2ml/min, react at ambient temperature with isocyanate-terminated polyimide, react and obtain organosilicon-polyimide material solution after 3 hours.Air dry oven solution being placed in 240 DEG C removes organosilicon-polyimide material that desolventizing obtains yellow for dry 6 hours.
Obtained organosilicon-polyimide material content of polysiloxane is 25.2%, polyimide segment content is 55.3%, amide functional mass contg 6.2%, initial decomposition temperature is higher than 280 DEG C, 5% mass loss temperature is more than 320 DEG C, contact angle reaches 105 °, in strong polar organic solvent, show good solvability.
Embodiment 3
In 250ml there-necked flask, add 16.0gPAPI and 30g toluene and add magneton unlatching magnetic stirring apparatus and stir, connect reflux condensing tube and nitrogen protection device subsequently, the oil bath pan being placed in 45 DEG C heats.
Take 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride 11.5g is dissolved in 120gN, N-N,N-DIMETHYLACETAMIDE, is added drop-wise in there-necked flask with the speed of 3ml/min with the N,N-dimethylacetamide solution of constant pressure funnel by pyromellitic acid dianhydride.To there-necked flask, solution no longer includes after gas produces and stops heating, obtains the isocyanate-terminated polyimide solution of red-brown clear, is cooled to room temperature set aside for use.
Take polydimethylsiloxane type hydroxy silicon oil 13.7g that 0.8g gram of dibutyl tin laurate and hydroxy radical content are 6% to mix and be placed in constant pressure funnel, be added drop-wise in there-necked flask with the speed of 2ml/min, react at ambient temperature with isocyanate-terminated polyimide, react and obtain organosilicon-polyimide material solution after 3 hours.Air dry oven solution being placed in 240 DEG C removes organosilicon-polyimide material that desolventizing obtains yellow for dry 6 hours.
Obtained organosilicon-polyimide material content of polysiloxane is 35.7%, polyimide segment content is 47.6%, amide functional mass contg 5.3%, initial decomposition temperature is higher than 280 DEG C, 5% mass loss temperature is more than 320 DEG C, contact angle reaches 102 °, in strong polar organic solvent, show good solvability.
Embodiment 4
In 250ml there-necked flask, add 25.0gMDI and 40g m-xylene and add magneton unlatching magnetic stirring apparatus and stir, connect reflux condensing tube and nitrogen protection device subsequently, the oil bath pan being placed in 45 DEG C heats.
Take pyromellitic acid dianhydride 17.4g and be dissolved in 120gN, N-N,N-DIMETHYLACETAMIDE, be added drop-wise in there-necked flask with the speed of 3ml/min with the N,N-dimethylacetamide solution of constant pressure funnel by pyromellitic acid dianhydride.To there-necked flask, solution no longer includes after gas produces and stops heating, obtains the isocyanate-terminated polyimide solution of red-brown clear, is cooled to room temperature set aside for use.
Take polydimethylsiloxane type hydroxy silicon oil 11.3g that 1g gram of dibutyl tin laurate and hydroxy radical content are 6% to mix and be placed in constant pressure funnel, be added drop-wise in there-necked flask with the speed of 2ml/min, react at ambient temperature with isocyanate-terminated polyimide, react and obtain organosilicon-polyimide material solution after 3 hours.Air dry oven solution being placed in 240 DEG C removes organosilicon-polyimide material that desolventizing obtains yellow for dry 2 hours.
Obtained organosilicon-polyimide material content of polysiloxane is 24.2%, polyimide segment content is 65.1%, amide functional mass contg 3.6%, initial decomposition temperature is higher than 280 DEG C, 5% mass loss temperature is more than 320 DEG C, contact angle reaches 101 °, in strong polar organic solvent, show good solvability.
Claims (8)
1. a preparation method for organosilicon and polyimide material, is characterized in that:
The massfraction of material chemical constitution is: polynary fragrant acid anhydride 10 ~ 30 parts, intensive polar solvent 50 ~ 300 parts, polyisocyanates 10 ~ 25 parts, weak polar solvent 10 ~ 60 parts, hydroxy silicon oil 0 ~ 25 part, catalyzer 0.5 ~ 2 part, and preparation process comprises:
(1) polynary fragrant acid anhydride and polyisocyanates react and prepare isocyanate-terminated polyimide
The intensive polar solvent solution of polynary fragrant acid anhydride and the weak polar solvent solution of polyisocyanates is prepared under room temperature, the weak polar solvent solution of polyisocyanates is joined in container, under nitrogen protection, the oil bath heating of 35 ~ 50 DEG C, pressure is added polynary fragrant acid anhydride intensive polar solvent solution after solution temperature is constant, after generating without gas to solution, stop heating obtaining isocyanate-terminated polyimide solution;
(2) synthesis of organosilicon-polyimide material
Hydroxy silicon oil and catalyst mixed liquid are added drop-wise under room temperature in the product that step (1) obtains, react and obtain organosilicon-polyimide material solution after 2 ~ 4 hours, dry 2 ~ 4 hours of the air dry oven being placed in 200 ~ 240 DEG C obtains organosilicon-polyimide material except desolventizing.
2. the preparation method of organosilicon according to claim 1 and polyimide material, is characterized in that: the described dropping VDE rate of addition in step (1) and step (2) controls to be 1 ~ 3ml/min.
3. the preparation method of organosilicon according to claim 1 and polyimide material, it is characterized in that: described polynary fragrant acid anhydride is pyromellitic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-xenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-oxydiphthalic, 3,3 ', 4,4 '-xenyl sulfone tetracarboxylic dianhydride, mellitic acid three acid anhydride, three trimellitic acid 1,2-anhydrides-1,3, one in 5-benzene three ester or 1,3,5-tri-oxygen-three (4-phthalic anhydride) benzene or mixture.
4. the preparation method of organosilicon according to claim 1 and polyimide material, is characterized in that: described intensive polar solvent is N-Methyl pyrrolidone, DMF, N,N-dimethylacetamide or dimethyl sulfoxide (DMSO); Described weak polar solvent is benzene, toluene or dimethylbenzene.
5. the preparation method of organosilicon according to claim 1 and polyimide material, it is characterized in that: described polyisocyanates is diphenylmethanediisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate or polyphenyl polymethylene polyisocyanates.
6. the preparation method of organosilicon according to claim 1 and polyimide material, is characterized in that: described catalyzer is one in stannous octoate, dibutyl tin laurate or Di-n-Butyl Amine or mixture.
7. the preparation method of organosilicon according to claim 1 and polyimide material, is characterized in that: described hydroxy silicon oil is one in polydimethylsiloxane type hydroxy silicon oil, polyphenyl methyl siloxane type hydroxy silicon oil or mixture; Hydroxyl Content in Hydroxysilicone fluid is 6.0 ~ 12.0%.
8. the preparation method of organosilicon according to claim 1 and polyimide material, it is characterized in that: contained by acid anhydride base amount of substance contained by described polynary fragrant acid anhydride and hydroxy silicon oil, the amount sum of hydroxylated material equals isocyanate group amount of substance contained by polyisocyanates, and the ratio of hydroxyl and acid anhydride base amount of substance is between 0.0:1.0 ~ 0.4:0.6.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109401637A (en) * | 2017-08-18 | 2019-03-01 | 菲森建设株式会社 | Steel pipe manufacture cementing compositions, compound galvanized steel plain sheet and its manufacturing method comprising it |
| CN109679495A (en) * | 2018-12-14 | 2019-04-26 | 江南大学 | A kind of preparation method of the modified PDMS silicone resin of fire resistant polyimide |
| CN110229340A (en) * | 2019-06-17 | 2019-09-13 | 中国科学院宁波材料技术与工程研究所 | A kind of polyimide aerogels and preparation method thereof based on silane hydrophobically modified |
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| CN102617857A (en) * | 2012-04-16 | 2012-08-01 | 上海交通大学 | Polyimide and preparation process thereof |
| CN104031241A (en) * | 2013-03-09 | 2014-09-10 | 东莞市长安东阳光铝业研发有限公司 | Preparing method of organosilicon-modified polyurethane-imide material and applications of the material |
| CN104844779A (en) * | 2015-05-18 | 2015-08-19 | 哈尔滨工程大学 | Preparation method for high-strength organosilicone and polyimide compound foam |
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- 2015-09-25 CN CN201510617626.1A patent/CN105175739A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102617857A (en) * | 2012-04-16 | 2012-08-01 | 上海交通大学 | Polyimide and preparation process thereof |
| CN104031241A (en) * | 2013-03-09 | 2014-09-10 | 东莞市长安东阳光铝业研发有限公司 | Preparing method of organosilicon-modified polyurethane-imide material and applications of the material |
| CN104844779A (en) * | 2015-05-18 | 2015-08-19 | 哈尔滨工程大学 | Preparation method for high-strength organosilicone and polyimide compound foam |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109401637A (en) * | 2017-08-18 | 2019-03-01 | 菲森建设株式会社 | Steel pipe manufacture cementing compositions, compound galvanized steel plain sheet and its manufacturing method comprising it |
| CN109401637B (en) * | 2017-08-18 | 2021-03-02 | 菲森建设株式会社 | Binding composition for manufacturing steel pipe, composite galvanized steel sheet containing same, and manufacturing method thereof |
| CN109679495A (en) * | 2018-12-14 | 2019-04-26 | 江南大学 | A kind of preparation method of the modified PDMS silicone resin of fire resistant polyimide |
| CN110229340A (en) * | 2019-06-17 | 2019-09-13 | 中国科学院宁波材料技术与工程研究所 | A kind of polyimide aerogels and preparation method thereof based on silane hydrophobically modified |
| CN110229340B (en) * | 2019-06-17 | 2022-03-08 | 中国科学院宁波材料技术与工程研究所 | Polyimide aerogel based on silane hydrophobic modification and preparation method thereof |
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Application publication date: 20151223 |