CN105086449B - Phosphorus-containing POSS (polyhedral oligomeric silsesquioxane) flame-retardant bismaleimide resin and preparation method thereof - Google Patents
Phosphorus-containing POSS (polyhedral oligomeric silsesquioxane) flame-retardant bismaleimide resin and preparation method thereof Download PDFInfo
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- CN105086449B CN105086449B CN201510578650.9A CN201510578650A CN105086449B CN 105086449 B CN105086449 B CN 105086449B CN 201510578650 A CN201510578650 A CN 201510578650A CN 105086449 B CN105086449 B CN 105086449B
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- silsesquioxane
- hydroxyphenyls
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/549—Silicon-containing compounds containing silicon in a ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention provides a phosphorus-containing POSS (polyhedral oligomeric silsesquioxane) flame-retardant bismaleimide resin and a preparation method thereof. The resin is composed of the following components in parts by mass: 100 parts of diphenylmethane bismaleimide, 50-100 parts of diallyl bisphenol A and 1-20 parts of poly(di(4-hydroxyphenyl)phenylphosphate) substituted chloropropyl silsesquioxane. Under the synergistic effects of the phosphorus and silicon in the poly(di(4-hydroxyphenyl)phenylphosphate) substituted chloropropyl silsesquioxane, the poly(di(4-hydroxyphenyl)phenylphosphate) substituted chloropropyl silsesquioxane can inhibit the combustion of the resin and promote the formation of the compact carbon layer, so that the resin generates a small amount of smoke and does not generate any toxic gas or corrosive gas in the combustion process and conforms to the environmental requirements. The poly(di(4-hydroxyphenyl)phenylphosphate) substituted chloropropyl silsesquioxane can react with the bismaleimide resin, and has favorable compatibility with the resin. Thus, the prepared bismaleimide resin system has the advantages of excellent mechanical properties, high flame retardancy and high temperature resistance, and can be used as an ablation-resistant material.
Description
Technical field
The invention belongs to advanced compound materials science domain, especially a kind of bimaleimide resin and its preparation
Method.
Background technology
Bimaleimide resin is the high-performance thermosetting resin matrix of the active double bond of a class, is widely used in handing over
The fields such as logical transport, Aero-Space, mechano-electronic.As macromolecular material is in the extensive use of every field, people are hindered it
Combustion property, self-extinguishment requirement more and more higher, therefore flame-retardant modified research and development is carried out to BMI there is important meaning
Justice.At present, addition packing type fire retardant is to improve the Main Means of resin matrix fire resistance, but most of fire retardants and resin
Matrix compatibility is poor, and while causing resins fire retardant performance to improve, mechanical property is greatly lowered.Therefore, span is improved to come
While acid imide anti-flammability, its excellent mechanical property can be kept to turn into the focus and difficult point of research at present again.
The content of the invention
In order to overcome the deficiencies in the prior art, the present invention provides a kind of high tenacity flame retardant type bimaleimide resin, interior
Containing a kind of phosphorous POSS based flameproofings of response type, POSS as a kind of potential hybrid Silicone-containing Flame Retardant, with
Resin matrix has good compatibility, and can connect upper various active or nonactive group by MOLECULE DESIGN, assigns its anti-
Ying Xingyu features, the fire retardant can occur condensation reaction with bimaleimide resin, improve phosphorous POSS based flameproofings
With the compatibility of bimaleimide resin；Simultaneously as the synergy of P elements and element silicon so that BMI
The anti-flammability of resin to larger raising.Therefore, the phosphorous POSS based flameproofings modified bismaleimide resin system, has
Excellent mechanical property and fire resistance, can be as ablation resistant material, to widening its application tool in high-performance engineering field
There is important meaning, make prepared resin that both there is excellent mechanical property, and with good fire resistance and heat resistance,
Can be used as ablation resistant material.
The technical solution adopted for the present invention to solve the technical problems is：A kind of phosphorous POSS flame retardant types BMI
Resin, by mass, including 100 parts of diphenyl-methane type BMIs, 50~100 parts of diallyl bisphenols and 1~20
Many (two (4- hydroxyphenyls) phenyl phosphonic acid esters) substitution chloropropyl silsesquioxane of part.
Wherein, the structural formula of diphenyl-methane type BMI is as follows：
The structural formula of diallyl bisphenol is as follows：
The structural formula of many (two (4- hydroxyphenyls) phenyl phosphonic acid esters) substitution chloropropyl silsesquioxane is as follows：
The present invention also provides a kind of preparation method of above-mentioned phosphorous POSS flame retardant types bimaleimide resin, including following
Step：
Step 1：Based on molal quantity, by 1 part of chloropropyl POSS, 4~10 parts of O, O- bis- (4- (hydroxyl) phenyl) Phenylphosphine
Acid esters, after 100~2000 parts of DMF mixed dissolution, 10~100 parts of triethylamines of addition, 1~5 part of KI,
Reacted 6~12 hours at 60~80 DEG C, then solvent evaporated, respectively with dilute hydrochloric acid solution that mass concentration is 1% and distillation
Water washing is respectively washed twice, and after recrystallization, obtains white crystal many (two (4- hydroxyphenyls) phenyl phosphonic acid esters) substitution chloropropyl times
Half siloxanes；
Step 2：By mass, 100 parts of diphenyl-methane type BMIs and 50~100 parts of diallyl bis-phenols are weighed
A, melts and stirs in 120~150 DEG C of heating, adds (two (4- hydroxyphenyls) phenyl phosphonic acid esters) more than 1~20 part substitution chlorine
Propylsilsesquioxane, pours at 130 DEG C in the mould for preheating more than 30min after stirring, and is put into 140~160 DEG C true
In empty van, deaeration laggard row order section elevated cure, curing process be incubated at being followed successively by 180 DEG C 2h, be incubated at 200 DEG C 2h, 220 DEG C
Lower insulation 2h, then cooling and demolding, h is post-processed at 250 DEG C.
The beneficial effects of the invention are as follows：Contain many (two (4- hydroxyphenyls) phenyl in bimaleimide resin of the invention
Phosphonate ester) substitution chloropropyl silsesquioxane, resin matrix curing reaction is may participate in, so as to improve fire retardant with resin matrix phase
Capacitive, while the excellent mechanical property of bimaleimide resin can be kept.When resin burns, due to many (two (4- oxybenzenes
Base) phenyl phosphonic acid esters) replace P elements and the cooperative effect of element silicon in chloropropyl silsesquioxane, can not only catch gas phase
In flammable H, OH, also promote the formation of resin burning surface densification layer of charcoal, completely cut off flame straight with resin matrix
Contact, so as to improve the fire resistance of resin.
Brief description of the drawings
Fig. 1 is resin solidification reaction mechanism schematic diagram.
Specific embodiment
The present invention is further described with reference to the accompanying drawings and examples, and the present invention includes but are not limited to following implementations
Example.
The present invention replaces chlorine third using diallyl bisphenol as toughener, with many (two (4- hydroxyphenyls) phenyl phosphonic acid esters)
Base silsesquioxane is modified as reactive flame retardant to diphenyl-methane type BMI.
By mass, the resin is double by 100 parts of diphenyl-methane type BMIs, 50~100 parts of diallyl
Phenol A, 1-20 part of many (two (4- hydroxyphenyls) phenyl phosphonic acid esters) substitution chloropropyl silsesquioxane composition.
Wherein, the structural formula of diphenyl-methane type BMI is as follows：
The structural formula of diallyl bisphenol is as follows：
The structural formula of many (two (4- hydroxyphenyls) phenyl phosphonic acid esters) substitution chloropropyl silsesquioxane is as follows：
The present invention replaces chloropropyl silsesquioxane as reaction-type flame-retarding using many (two (4- hydroxyphenyls) phenyl phosphonic acid esters)
Condensation reaction can occur with diallyl bisphenol under agent, high temperature, and diallyl bisphenol can occur Diels- with resin matrix
Alder reacts, so that many (two (4- hydroxyphenyls) phenyl phosphonic acid esters) substitution chloropropyl silsesquioxane is connected to resin web
Network, improves its compatibility with resin, not only causes that resins fire retardant obtains larger raising, while its mechanical property is also obtained
Larger raising.Its curing kinetics is as shown in Figure 1.
First, many (two (4- hydroxyphenyls) phenyl phosphonic acid esters) substitution chloropropyl silsesquioxane is prepared, is then anti-with it
Type fire retardant is answered, the melt blending together with diallyl bisphenol, diphenyl-methane type BMI, pre-polymerization, shaping.Specifically
Method is as follows：
Step 1：Based on molal quantity, by 1 part of chloropropyl POSS, 4~10 parts of O, O- bis- (4- (hydroxyl) phenyl) Phenylphosphine
Acid esters, in 100~2000 parts of DMF addition there-necked flask, after dissolving, adds 10~100 parts of triethylamines, 1
~5 parts of KI, reacts 6~12 hours at 60~80 DEG C of water-bath, and solvent evaporated, is respectively 1% with mass fraction after completion of the reaction
Dilute hydrochloric acid solution and distilled water are respectively washed twice, and after recrystallization, obtain white crystal many (two (4- hydroxyphenyls) phenyl phosphonic acid esters)
Substitution chloropropyl silsesquioxane.
Step 2：By mass, 100 parts of diphenyl-methane type BMIs, 50~100 parts of diallyl bisphenols are weighed
It is put into beaker, in 120~150 DEG C of heating meltings, stirs, adds (two (4- hydroxyphenyls) phenyl-phosphonic acids more than 1~20 part
Ester) substitution chloropropyl silsesquioxane, after stirring, it is poured at 130 DEG C in the mould for preheating more than 30min, it is put into
In 140~160 DEG C of vacuum tank, after deaeration, being put into air dry oven carries out stage elevated cure, and curing process is 180 DEG C/2h
+ 200 DEG C/2h+220 DEG C/2h, cooling, after the demoulding, then post processing 4h is obtained final product at 250 DEG C.
Embodiment 1：
Step 1：By 0.001mol chloropropyls POSS, 0.006mol O, O- bis- (4- (hydroxyl) phenyl) phenyl phosphonic acid esters,
The DMF of 0.7mol is added in there-necked flask, after dissolving, addition 0.02mol triethylamines, and 0.002mol KI,
Reacted 8 hours at 80 DEG C of water-bath, solvent is boiled off after completion of the reaction, washed with watery hydrochloric acid and distilled water respectively, after recrystallization,
Obtain many (two (4- hydroxyphenyls) phenyl phosphonic acid esters) substitution chloropropyl silsesquioxane.
Step 2：By mass, 100 parts of diphenyl-methane type BMIs, 60 parts of diallyl bisphenols are weighed to be put into
In beaker, in 120~150 DEG C of heating meltings, stir, add (two (4- hydroxyphenyls) phenyl phosphonic acid esters) more than 10 parts substitution chlorine
Propylsilsesquioxane, after stirring, is poured at 130 DEG C in the mould for preheating more than 30min, is put into 140~160 DEG C
Vacuum tank in, after deaeration, being put into air dry oven carries out stage elevated cure, and curing process is 180 DEG C/2h+200 DEG C/2h+
220 DEG C/2h, cooling, after the demoulding, then post processing 4h is obtained final product at 250 DEG C.
Embodiment 2：
Step 1：By 0.001mol chloropropyls POSS, 0.010mol O, O- bis- (4- (hydroxyl) phenyl) phenyl phosphonic acid esters,
The DMF of 1.0mol is added in there-necked flask, after dissolving, addition 0.02mol triethylamines, and 0.004mol KI,
Reacted 6 hours at 80 DEG C of water-bath, solvent is boiled off after completion of the reaction, washed with watery hydrochloric acid and distilled water respectively, after recrystallization,
Obtain many (two (4- hydroxyphenyls) phenyl phosphonic acid esters) substitution chloropropyl silsesquioxane.
Step 2：With embodiment 1.
Embodiment 3：
Step 1：With embodiment 1.
Step 2：By mass, 100 parts of diphenyl-methane type BMIs, 75 parts of diallyl bisphenols are weighed to be put into
In beaker, in 120~150 DEG C of heating meltings, stir, add (two (4- hydroxyphenyls) phenyl phosphonic acid esters) more than 5 parts substitution chlorine
Propylsilsesquioxane, after stirring, is poured at 130 DEG C in the mould for preheating more than 30min, is put into 140~160 DEG C
Vacuum tank in, after deaeration, being put into air dry oven carries out stage elevated cure, and curing process is 180 DEG C/2h+200 DEG C/2h+
220 DEG C/2h, cooling, after the demoulding, then post processing 4h is obtained final product at 250 DEG C.
Embodiment 4：
Step 1：With embodiment 2.
Step 2：By mass, 100 parts of diphenyl-methane type BMIs, 80 parts of diallyl bisphenols are weighed to be put into
In beaker, in 120~150 DEG C of heating meltings, stir, add (two (4- hydroxyphenyls) phenyl phosphonic acid esters) more than 3 parts substitution chlorine
Propylsilsesquioxane, after stirring, is poured at 130 DEG C in the mould for preheating more than 30min, is put into 140~160 DEG C
Vacuum tank in, after deaeration, being put into air dry oven carries out stage elevated cure, and curing process is 180 DEG C/2h+200 DEG C/2h+
220 DEG C/2h, cooling, after the demoulding, then post processing 4h is obtained final product at 250 DEG C.
Embodiment 5：
Step 1：With embodiment 2.
Step 2：By mass, 100 parts of diphenyl-methane type BMIs, 60 parts of diallyl bisphenols are weighed to be put into
In beaker, in 120~150 DEG C of heating meltings, stir, add (two (4- hydroxyphenyls) phenyl phosphonic acid esters) more than 5 parts substitution chlorine
Propylsilsesquioxane, after stirring, is poured at 130 DEG C in the mould for preheating more than 30min, is put into 140~160 DEG C
Vacuum tank in, after deaeration, being put into air dry oven carries out stage elevated cure, and curing process is 180 DEG C/2h+200 DEG C/2h+
220 DEG C/2h, cooling, after the demoulding, then post processing 4h is obtained final product at 250 DEG C.
Above content is to combine specific embodiment to the further description done by the present invention, it is impossible to assert this
The specific embodiment of invention is only limitted to this, though embodiment of the invention is undisclosed, those skilled in the art can be pre-
See and determine.
Claims (2)
1. a kind of phosphorous POSS flame retardant types bimaleimide resin, it is characterised in that：By mass, including 100 parts of hexichol first
Alkane type BMI, 50~100 parts of diallyl bisphenol and 1~20 part many (two (4- hydroxyphenyls) phenyl-phosphonic acids
Ester) substitution chloropropyl silsesquioxane；The structural formula of described diphenyl-methane type BMI is as follows：
The structural formula of diallyl bisphenol is as follows：
The structural formula of many (two (4- hydroxyphenyls) phenyl phosphonic acid esters) substitution chloropropyl silsesquioxane is as follows：
2. a kind of preparation method of phosphorous POSS flame retardant types bimaleimide resin described in claim 1, it is characterised in that bag
Include following step：
Step 1：Based on molal quantity, by 1 part of chloropropyl POSS, 4~10 parts of O, O- bis- (4- (hydroxyl) phenyl) phenyl phosphonic acid esters,
After 100~2000 parts of DMF mixed dissolution, 10~100 parts of triethylamines are added, 1~5 part of KI, 60~
Reacted 6~12 hours at 80 DEG C, then solvent evaporated, respectively with dilute hydrochloric acid solution that mass concentration is 1% and distillation water washing
Respectively wash twice, after recrystallization, obtain white crystal many (two (4- hydroxyphenyls) phenyl phosphonic acid esters) substitution chloropropyl silsesquioxane
Alkane；
Step 2：By mass, 100 parts of diphenyl-methane type BMIs and 50~100 parts of diallyl bisphenols are weighed,
120~150 DEG C of heating are melted and stirred, and add (two (4- hydroxyphenyls) phenyl phosphonic acid esters) more than 1~20 part substitution chloropropyl
Silsesquioxane, pours at 130 DEG C in the mould for preheating more than 30min after stirring, and is put into 140~160 DEG C of vacuum tank
In, deaeration laggard row order section elevated cure, curing process is incubated 2h, 2h is incubated at 200 DEG C, is protected at 220 DEG C at being followed successively by 180 DEG C
Warm 2h, then cooling and demolding, 4h is post-processed at 250 DEG C.
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| CN201510578650.9A CN105086449B (en) | 2015-09-11 | 2015-09-11 | Phosphorus-containing POSS (polyhedral oligomeric silsesquioxane) flame-retardant bismaleimide resin and preparation method thereof |
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| CN201510578650.9A CN105086449B (en) | 2015-09-11 | 2015-09-11 | Phosphorus-containing POSS (polyhedral oligomeric silsesquioxane) flame-retardant bismaleimide resin and preparation method thereof |
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| CN108034246A (en) * | 2017-12-28 | 2018-05-15 | 南京鸿瑞塑料制品有限公司 | A kind of fire-retardant non-reinforcing PA66 composite materials of phosphorus silicon and preparation method thereof |
| CN108384003B (en) * | 2018-01-24 | 2021-06-15 | 航天科工防御技术研究试验中心 | Modified bismaleimide resin and preparation method thereof |
| US10752776B2 (en) | 2018-09-19 | 2020-08-25 | International Business Machines Corporation | Cyclic bio-renewable flame retardants |
| CN109575076B (en) * | 2018-11-08 | 2020-11-27 | 中北大学 | Preparation of phosphorus-containing bismaleimide and application of phosphorus-containing bismaleimide in flame-retardant epoxy resin |
| CN110591544B (en) * | 2019-09-27 | 2021-02-19 | 四川羽玺新材料股份有限公司 | High-hardness and low-haze UV hardened layer coating liquid |
| CN110982264A (en) * | 2019-12-23 | 2020-04-10 | 哈尔滨工业大学 | Preparation method of modified cyanate ester resin with atomic oxygen irradiation resisting characteristic |
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| CN102079874A (en) * | 2009-11-27 | 2011-06-01 | 南京理工大学 | Preparation method of cage-type silsesquioxane-containing low-dielectric cyanate hybrid resin |
| CN101863854A (en) * | 2010-06-29 | 2010-10-20 | 沈阳药科大学 | Synthesis method of 2-(3-cyan-4-isobutoxy) phenyl-4-methyl-5-thiazole formic acid |
| KR20150100765A (en) * | 2012-12-21 | 2015-09-02 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | Curable silsesquioxane polymers, compositions, articles, and methods |
| CN104448830B (en) * | 2014-11-24 | 2017-04-05 | 上海工程技术大学 | A kind of phosphorus silicon composite flame-retardant agent and its preparation method and application |
| CN104530430B (en) * | 2015-01-09 | 2017-02-01 | 西北工业大学 | High-tenacity flame-retardant bismaleimide resin and preparation method thereof |
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