CN107629208A - A kind of preparation method of Polyimide foams - Google Patents
A kind of preparation method of Polyimide foams Download PDFInfo
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- CN107629208A CN107629208A CN201710935625.0A CN201710935625A CN107629208A CN 107629208 A CN107629208 A CN 107629208A CN 201710935625 A CN201710935625 A CN 201710935625A CN 107629208 A CN107629208 A CN 107629208A
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Abstract
The invention discloses a kind of preparation method of Polyimide foams, belong to field of polymer material preparing technology.Pyromellitic dianhydride, poly methylene poly phenyl poly isocyanate and polar solvent are added reactor by technical solution of the present invention first, constant temperature stirring reaction, obtain performed polymer, calcium oxide, absolute ethyl alcohol, foam stabilizer, thinner and coupling agent are stirred again, obtain mixed aid, then performed polymer and mixed aid are mixed, temperature programming after cooling, and absolute ethyl alcohol and water are added under constant temperature stirring, then reacted obtained slurry, through injection molding after, after temperature programming solidification, cooling, the demoulding, produces Polyimide foams.Polyimide foams prepared by technical solution of the present invention are improving its thermal stability simultaneously, and its mechanical property significantly improves, and promote it in multi-field popularization and application.
Description
Technical field
The invention discloses a kind of preparation method of Polyimide foams, belongs to high polymer material technology of preparing neck
Domain.
Background technology
With the rapid development of the sciemtifec and technical spheres such as Aero-Space, navigation, conventional foams（Such as PS, PU, PVC）Strong
Degree, rigidity and heat resistance etc. can not meet requirement, therefore develop high-performance foam plastics grinding as the field
Study carefully direction and focus.Characteristic applied to the material in field of aerospace and military boats and ships is with inherent flame retardant, environmental protection
The excellent combination properties such as nontoxic, tolerable temperature scope is wide, thermal conductivity factor is low, resistance to irradiation, light, easy processing installation, Ke Yi
Long service under the extreme conditions such as superhigh temperature, ultralow temperature, high salt fog, very noisy, deep-etching, intense radiation, have high reliable
Property and quality assurance.The good combination property of polyimides makes it gain great popularity, because it has light, fire-retardant, radiation hardness, smoke
The advantages that rate is low, environmentally friendly, shockproof, the fields such as space flight, aviation, naval vessel, high ferro, laser, nuclear power are widely used to, but it is integrated
Performance still has greatly improved space.
Padded coaming directly contacts with product can play cushioning effect, and its performance directly influences packaging material to production
The protection of product.As the representative of novel foam material, Polyimide foams have light, fire-retardant, radiation hardness, ring because of it
The good characteristic such as guarantor, shockproof, gets growing concern in Aero-Space, electronic apparatus and information industry field.Space flight
Product also requires that amortizing packaging material has good heat endurance and dimensional stability during transport and preservation, can
The test of alternating hot and cold is resistant to, retention property is stable in changing environment, to ensure the reliability of product quality, security, prolongs
Long storage life.The preparation of polyimide foam at present mainly has one-step method, two-step method and pre-polymerization method.One-step preparation process letter
It is single, the cycle is short, instrument and equipment is easy to operate, the foam aperture of preparation uniformly, stable performance, but raw material proportioning influences on foam structure
It is very big, and be difficult the release of amount of heat in control foaming process.Foamed plastics combination property prepared by two-step method is preferable, but makes
Standby complex process, molding cycle length, because heat-blocking action causes polyimide foam top layer and inner homogeneous poor.Pre-polymerization method, work
Skill is simple, by controlling performed polymer viscosity, effectively controls foaming process, prepares polyimide foam, is controlled in foam structure
Aspect prepares polyimide foam than one-step method and is more easily implemented, while reduces the generation of side reaction, carries to a certain extent
The combination property of high polyimide foam, but still do not reach preferable effect.
Therefore, further improve Polyimide foams mechanical property and thermal stability, could promote its popularization and
Using.
The content of the invention
The present invention solves the technical problem of：For traditional Polyimide foams heat endurance and mechanical property
A kind of the problem of bad, there is provided preparation method of Polyimide foams.
In order to solve the above-mentioned technical problem, the technical solution adopted in the present invention is：
（1）Count in parts by weight, take 10~20 parts of pyromellitic dianhydrides, 15~20 parts of polymethylene polyphenyl polyisocyanic acid successively
Ester, 80~150 parts of polar solvents, 8~10 parts of calcium oxide, 15~20 parts of water, 10~15 parts of absolute ethyl alcohols, 1~3 portion of foam stabilizer, 4
~6 portions of thinners, 1~3 part of coupling agent；
（2）Pyromellitic dianhydride, poly methylene poly phenyl poly isocyanate and polar solvent are first added into reactor, constant temperature stirring
Reaction, obtains performed polymer；
（3）Calcium oxide, absolute ethyl alcohol, foam stabilizer, thinner and coupling agent are stirred, obtain mixed aid；
（4）After performed polymer and mixed aid hybrid reaction, cooling, then then stirred through temperature programming to 25~30 DEG C in constant temperature
Mix and water is added under state, after constant-temperature enclosed stirring reaction, obtain slurry；
（5）Gained slurry is injected in mould, after temperature programming solidification, room temperature is naturally cooled to, is stripped, produces polyimides bubble
Foam material.
The polar solvent is any one in N,N-dimethylformamide or dimethyl sulfoxide (DMSO).
The calcium oxide can also be pretreatment calcium oxide, and specific preprocessing process is：Calcium oxide and glycerine are pressed into quality
Than for 10：1~20：1 adds ball mill, 4~6h of ball milling mixing, obtains pretreatment calcium oxide.
The foam stabilizer is any one in neopelex, silicone oil AK8803 or silicone oil AK8807.
The thinner is any one in castor oil, machine oil or diesel oil.
The coupling agent is appointing in silane resin acceptor kh-550, silane coupler KH-560 or Silane coupling reagent KH-570
Meaning is a kind of.
The beneficial effects of the invention are as follows：
（1）Technical solution of the present invention is using water as foaming agent, by adding calcium oxide in Polyimide foams preparation process,
During the course of the reaction, a part of water and isocyanates reaction generation carbon dioxide, so as to play foaming effect, and another portion
Divide water and calcium oxide reaction generation calcium hydroxide, calcium hydroxide may act as the effect of carbon dioxide storage agent, elder generation and carbon dioxide
Reaction generation calcium carbonate, and under excess carbon dioxide and water condition, further reaction generation calcium bicarbonate and by carbon dioxide
It is stored in system, then coordinates the strict control in whole course of reaction to temperature, so that stable system foams, makes in system
Portion forms uniform cell structure, and during down-stream elevated cure, calcium bicarbonate starts under relatively lower temp
Decompose, and generate water, carbon dioxide and calcium carbonate, water can further react with the isocyanates remained in system, make reaction more
Fully, caused carbon dioxide can further function as the effect of stable foaming, product stability is effectively improved, finally
Calcium carbonate is scattered in foam structure inwall, plays enhancing effect, improve the mechanical property of material as filler；
（2）Technical solution of the present invention pre-processes by using glycerine to calcium oxide, and glycerine has good wettability, can
It is effectively improved dispersive property of the calcium oxide in system, and organic matter is to the wetability of inorganic oxide calcium in product, in addition, sweet
Oil is polyol structure, can be reacted with isocyanates in system, generate corresponding polyurethanes, so that reaction system
Expansion rate obtains stability contorting, and product stability effectively improves.
Embodiment
It is 10 in mass ratio：1~20：1 adds calcium oxide and glycerine in ball grinder, and is 15 by ball material mass ratio：1~30：1
Zirconium oxide ball milling pearl is added, 2~4h of ball milling mixing, ball milling material is obtained, as pre-processes calcium oxide；Count, take successively in parts by weight
10~20 parts of pyromellitic dianhydrides, 15~20 parts of poly methylene poly phenyl poly isocyanates, 80~150 parts of polar solvents, 8~10
Part pretreatment calcium oxide, 15~20 parts of water, 10~15 parts of absolute ethyl alcohols, 1~3 portion of foam stabilizer, 4~6 portions of thinners, 1~3 part of idol
Join agent；First pyromellitic dianhydride, poly methylene poly phenyl poly isocyanate and polar solvent are added in reactor, are in temperature
65~75 DEG C, under the conditions of rotating speed is 300~400r/min, constant temperature 2~4h of stirring reaction, obtain performed polymer；Pretreatment is aoxidized again
Calcium, absolute ethyl alcohol, foam stabilizer, thinner and coupling agent with mixer be stirred 45 with 300~500r/min rotating speeds~
60min, obtain mixed aid；Then gained performed polymer and gained mixed aid are added in three-necked flask, and three-necked flask is moved
Enter in the ice-water bath that temperature is 2~4 DEG C, under the conditions of rotating speed is 400~600r/min, constant temperature stirring 10~20min of cooling, with
Three-necked flask immigration digital display is tested the speed constant temperature blender with magnetic force afterwards, 25~30 DEG C are warming up to 2~4 DEG C/min rate programs, with
It is 25~30 DEG C after temperature, under the conditions of rotating speed is 300~500r/min, adds water into three-necked flask, then by three-necked flask
It is closed, constant temperature 10~15min of stirring reaction, obtain slurry；Gained slurry is injected in mould, mould is placed in baking oven, with 3~
5 DEG C/min rate programs are warming up to 200~250 DEG C, 3~5h of heat preservation solidification, then mould is removed into baking oven, and standing naturally cools to
Room temperature, the demoulding, produces Polyimide foams.The polar solvent is in N,N-dimethylformamide or dimethyl sulfoxide (DMSO)
Any one.The foam stabilizer is any one in neopelex, silicone oil AK8803 or silicone oil AK8807.It is described
Thinner is any one in castor oil, machine oil or diesel oil.The coupling agent is silane resin acceptor kh-550, silane coupler
Any one in KH-560 or Silane coupling reagent KH-570.
Example 1
It is 20 in mass ratio：1 adds calcium oxide and glycerine in ball grinder, and is 30 by ball material mass ratio：1 adds zirconia ball
Pearl is ground, ball milling mixing 4h, ball milling material is obtained, as pre-processes calcium oxide；Count in parts by weight, take 20 parts of Pyromellitic Acids successively
Acid anhydride, 20 parts of poly methylene poly phenyl poly isocyanates, 150 parts of polar solvents, 10 parts of pretreatment calcium oxide, 20 parts of water, 15 parts of nothings
Water-ethanol, 3 portions of foam stabilizers, 6 portions of thinners, 3 parts of coupling agents；First by pyromellitic dianhydride, polymethylene polyphenyl polyisocyanic acid
Ester and polar solvent are added in reactor, are 75 DEG C in temperature, under the conditions of rotating speed is 400r/min, constant temperature stirring reaction 4h, are obtained
Performed polymer；Calcium oxide, absolute ethyl alcohol, foam stabilizer, thinner and coupling agent mixer will be pre-processed again with 500r/min rotating speeds
60min is stirred, obtains mixed aid；Then gained performed polymer and gained mixed aid are added in three-necked flask, and by three
Mouth flask is moved into the ice-water bath that temperature is 4 DEG C, and under the conditions of rotating speed is 600r/min, constant temperature stirring cools down 20min, then will
Three-necked flask moves into digital display and tested the speed constant temperature blender with magnetic force, and 30 DEG C are warming up to 4 DEG C/min rate programs, is 30 with after temperature
DEG C, under the conditions of rotating speed is 500r/min, water is added into three-necked flask, then three-necked flask is closed, constant temperature stirring reaction
15min, obtain slurry；Gained slurry is injected in mould, mould is placed in baking oven, 250 are warming up to 5 DEG C/min rate programs
DEG C, heat preservation solidification 5h, then mould is removed into baking oven, standing naturally cools to room temperature, is stripped, produces Polyimide foams.
The polar solvent is dimethyl sulfoxide (DMSO).The foam stabilizer is neopelex.The thinner is castor oil.It is described
Coupling agent is silane resin acceptor kh-550.
Example 2
Count in parts by weight, take 20 parts of pyromellitic dianhydrides, 20 parts of poly methylene poly phenyl poly isocyanates, 150 parts of poles successively
Property solvent, 20 parts of water, 15 parts of absolute ethyl alcohols, 3 portions of foam stabilizers, 6 portions of thinners, 3 parts of coupling agents；It is more first by pyromellitic dianhydride
Polymethylene polyphenyl polyisocyanates and polar solvent are added in reactor, are 75 DEG C in temperature, rotating speed is 400r/min conditions
Under, constant temperature stirring reaction 4h, obtain performed polymer；Again by absolute ethyl alcohol, foam stabilizer, thinner and coupling agent mixer with 500r/
Min rotating speeds are stirred 60min, obtain mixed aid；Then gained performed polymer and gained mixed aid are added in three-necked flask,
And move into three-necked flask in the ice-water bath that temperature is 4 DEG C, under the conditions of rotating speed is 600r/min, constant temperature stirring cooling 20min,
Then three-necked flask immigration digital display is tested the speed constant temperature blender with magnetic force, 30 DEG C are warming up to 4 DEG C/min rate programs, with after temperature
Spend for 30 DEG C, under the conditions of rotating speed is 500r/min, water is added into three-necked flask, then three-necked flask is closed, constant temperature stirring is anti-
15min is answered, obtains slurry；Gained slurry is injected in mould, mould is placed in baking oven, is warming up to 5 DEG C/min rate programs
250 DEG C, heat preservation solidification 5h, then mould is removed into baking oven, standing naturally cools to room temperature, is stripped, produces polyimide foam material
Material.The polar solvent is dimethyl sulfoxide (DMSO).The foam stabilizer is neopelex.The thinner is castor oil.
The coupling agent is silane resin acceptor kh-550.
Example 3
Count in parts by weight, take 20 parts of pyromellitic dianhydrides, 20 parts of poly methylene poly phenyl poly isocyanates, 150 parts of poles successively
Property solvent, 10 parts of calcium oxide, 20 parts of water, 15 parts of absolute ethyl alcohols, 3 portions of foam stabilizers, 6 portions of thinners, 3 parts of coupling agents；First by equal benzene
Tetracarboxylic acid anhydride, poly methylene poly phenyl poly isocyanate and polar solvent are added in reactor, are 75 DEG C in temperature, rotating speed is
Under the conditions of 400r/min, constant temperature stirring reaction 4h, performed polymer is obtained；Again by calcium oxide, absolute ethyl alcohol, foam stabilizer, thinner and idol
Connection agent is stirred 60min with mixer with 500r/min rotating speeds, obtains mixed aid；Then gained performed polymer and gained are mixed
Auxiliary agent is added in three-necked flask, and three-necked flask is moved into temperature and is in 4 DEG C of ice-water bath, in rotating speed be 600r/min conditions
Under, constant temperature stirring cooling 20min, then three-necked flask immigration digital display is tested the speed constant temperature blender with magnetic force, with 4 DEG C/min speed journeys
Sequence is warming up to 30 DEG C, with being 30 DEG C after temperature, under the conditions of rotating speed is 500r/min, adds water into three-necked flask, then by three
Mouth flask is closed, constant temperature stirring reaction 15min, obtains slurry；Gained slurry is injected in mould, mould is placed in baking oven, with 5
DEG C/min rate programs are warming up to 250 DEG C, heat preservation solidification 5h, then mould are removed into baking oven, standing naturally cools to room temperature, takes off
Mould, produce Polyimide foams.The polar solvent is dimethyl sulfoxide (DMSO).The foam stabilizer is DBSA
Sodium.The thinner is castor oil.The coupling agent is silane resin acceptor kh-550.
Comparative example：The Polyimide foams of Shanghai Industrial Co., Ltd. production.
The Polyimide foams of the gained of example 1 to 3 and comparative example product are subjected to performance detection, specific detection method
It is as follows：
1. heat endurance：Differential scanning calorimetry（DSC）Analysis：DSC1/500 using Mettler Toledo companies of Switzerland enters
Row DSC is tested, 10 DEG C/min of heating rate；Thermal weight loss（TG）Analysis：Using the TGA-50 types thermal weight loss point of Japanese Shimadzu Corporation
Analyzer determines the heat endurance of material.Under nitrogen protection, 10 DEG C/min of heating rate；Wherein T5%Represent polyimide foam heat
Temperature during weightlessness 5%, T10%Represent temperature during polyimide foam thermal weight loss 10%, R750Represent polyimide foam at 750 DEG C
Residual heavy rate；
2. mechanical property：Test specimen tensile property and compression performance are detected with electronic universal tester.
Specific testing result is as shown in table 1：
Table 1
| Detection project | Example 1 | Example 2 | Example 3 | Comparative example |
| T5%/℃ | 403.8 | 397.5 | 395.8 | 386.1 |
| T10%/℃ | 510.2 | 504.9 | 501.7 | 492.7 |
| R750/% | 67.3 | 65.4 | 62.8 | 55.2 |
| Tensile strength/MPa | 1.43 | 1.38 | 1.25 | 1.02 |
| Elongation at break/% | 19.87 | 15.64 | 14.73 | 10.32 |
| Compressive strength/MPa | 2.31 | 2.09 | 1.98 | 1.74 |
From the testing result of table 1, Polyimide foams prepared by technical solution of the present invention are improving its thermal stability
Meanwhile its mechanical property significantly improves, promote it in multi-field popularization and application.
Claims (6)
1. a kind of preparation method of Polyimide foams, it is characterised in that specifically preparation process is：
（1）Count in parts by weight, take 10~20 parts of pyromellitic dianhydrides, 15~20 parts of polymethylene polyphenyl polyisocyanic acid successively
Ester, 80~150 parts of polar solvents, 8~10 parts of calcium oxide, 15~20 parts of water, 10~15 parts of absolute ethyl alcohols, 1~3 portion of foam stabilizer, 4
~6 portions of thinners, 1~3 part of coupling agent；
（2）Pyromellitic dianhydride, poly methylene poly phenyl poly isocyanate and polar solvent are first added into reactor, constant temperature stirring
Reaction, obtains performed polymer；
（3）Calcium oxide, absolute ethyl alcohol, foam stabilizer, thinner and coupling agent are stirred, obtain mixed aid；
（4）After performed polymer and mixed aid hybrid reaction, cooling, then then stirred through temperature programming to 25~30 DEG C in constant temperature
Mix and water is added under state, after constant-temperature enclosed stirring reaction, obtain slurry；
（5）Gained slurry is injected in mould, after temperature programming solidification, room temperature is naturally cooled to, is stripped, produces polyimides bubble
Foam material.
A kind of 2. preparation method of Polyimide foams according to claim 1, it is characterised in that：The polarity is molten
Agent is any one in N,N-dimethylformamide or dimethyl sulfoxide (DMSO).
A kind of 3. preparation method of Polyimide foams according to claim 1, it is characterised in that：The calcium oxide
Can also be pretreatment calcium oxide, specific preprocessing process is：It is 10 in mass ratio by calcium oxide and glycerine：1~20：1 adds
Ball mill, 4~6h of ball milling mixing, obtain pretreatment calcium oxide.
A kind of 4. preparation method of Polyimide foams according to claim 1, it is characterised in that：The foam stabilizer
For any one in neopelex, silicone oil AK8803 or silicone oil AK8807.
A kind of 5. preparation method of Polyimide foams according to claim 1, it is characterised in that：The thinner
For any one in castor oil, machine oil or diesel oil.
A kind of 6. preparation method of Polyimide foams according to claim 1, it is characterised in that：The coupling agent
For any one in silane resin acceptor kh-550, silane coupler KH-560 or Silane coupling reagent KH-570.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109810251A (en) * | 2019-01-15 | 2019-05-28 | 哈尔滨工程大学 | A kind of preparation method of high-performance rigid polyimides heat insulation and acoustic absorption foam |
| CN110776741A (en) * | 2019-10-11 | 2020-02-11 | 东华大学 | High-low temperature resistant piezoresistive sensing polyimide composite aerogel and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101812232A (en) * | 2010-04-09 | 2010-08-25 | 北京航空航天大学 | Polyimide foam and preparation method thereof |
| CN102093714A (en) * | 2010-12-22 | 2011-06-15 | 北京航空航天大学 | Light flexible polymide foam material and preparation method thereof |
-
2017
- 2017-10-10 CN CN201710935625.0A patent/CN107629208A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101812232A (en) * | 2010-04-09 | 2010-08-25 | 北京航空航天大学 | Polyimide foam and preparation method thereof |
| CN102093714A (en) * | 2010-12-22 | 2011-06-15 | 北京航空航天大学 | Light flexible polymide foam material and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109810251A (en) * | 2019-01-15 | 2019-05-28 | 哈尔滨工程大学 | A kind of preparation method of high-performance rigid polyimides heat insulation and acoustic absorption foam |
| CN109810251B (en) * | 2019-01-15 | 2021-10-26 | 哈尔滨工程大学 | Preparation method of high-performance rigid polyimide heat-insulation sound-absorption foam |
| CN110776741A (en) * | 2019-10-11 | 2020-02-11 | 东华大学 | High-low temperature resistant piezoresistive sensing polyimide composite aerogel and preparation method thereof |
| CN110776741B (en) * | 2019-10-11 | 2021-12-21 | 东华大学 | High-low temperature resistant piezoresistive sensing polyimide composite aerogel and preparation method thereof |
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Application publication date: 20180126 |