CN106995581B - A kind of polybenzimidazoles, the combined modified phenolic resin foam of carboxy nitrile rubber and preparation method thereof - Google Patents
A kind of polybenzimidazoles, the combined modified phenolic resin foam of carboxy nitrile rubber and preparation method thereof Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
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- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
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- C08J2479/00—Characterised by the use 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 C08J2461/00 - C08J2477/00
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Abstract
The invention discloses a kind of polybenzimidazoles, the combined modified phenolic resin foam of carboxy nitrile rubber and preparation method thereof, are technically characterized in that, in parts by weight, are made of following raw material：50~60 parts of phenol-formaldehyde resin modified, simultaneously 15-20 parts of imidazoles of modified polyphenyl, 10-15 parts of carboxy nitrile rubber, 8-12 parts of Tween-80,10-12 parts and curing agent 5-15 parts of foaming agent.The present invention first introduces polybenzimidazoles alkyl-modified under alkaline condition, then it reacts the mixed phenol of naphthols and phenol to obtain phenol-formaldehyde resin modified with formaldehyde, finally phenol-formaldehyde resin modified, modified polyphenyl and imidazoles and carboxy nitrile rubber are blended, ternary blend systems are formed, final curing demoulds to obtain phenol-formaldehyde resin modified foam.
Description
Technical field
The present invention relates to phenolic resins field, specifically a kind of polybenzimidazoles, carboxy nitrile rubber, which are combined, to be changed
Property phenolic resin foam.
Background technique
Traditional organic polymer foam includes polystyrene foam, polyurethane foam etc., this kind of materials there are it is inflammable,
The disadvantages of heat is easily-deformable, thickness is toxic, fire protecting performance is poor.Phenol formaldehyde foam is a kind of emerging polymer thermal insulative material, with biography
System polymeric foam is compared, it has good thermal stability, nonflammable, good heat insulating, easy processing molding, good stability of the dimension
The advantages that, it is therefore widely used in the fields such as ship, building, aerospace.But phenol formaldehyde foam toughness is poor, is using
It is easy to break scaling-off in the process, the toughness of phenol formaldehyde foam can be improved by way of toughening, but the fire line of material can be made
It can decline.In addition, when the use temperature of phenol formaldehyde foam is more than 160 DEG C, it will thermal degradation occurs, material property is caused to decline.
Summary of the invention
To solve the above problems, the object of the present invention is to provide a kind of polybenzimidazoles, carboxy nitrile rubber are combined modified
Phenolic resin foam.
The present invention to achieve the above object, is achieved through the following technical solutions：
A kind of polybenzimidazoles, the combined modified phenolic resin foam of carboxy nitrile rubber, in parts by weight, by following raw material
Composition：50~60 parts of phenol-formaldehyde resin modified, simultaneously 15-20 parts of imidazoles of modified polyphenyl, 10-15 parts of carboxy nitrile rubber, Tween-80 8-
12 parts, 10-12 parts and curing agent 5-15 parts of foaming agent；
The foaming agent is pentane, n-hexane, normal heptane or petroleum ether；
The curing agent is p-methyl benzenesulfonic acid or camphorsulfonic acid；
The modified polyphenyl and imidazoles is prepared by following steps：In parts by weight, by polybenzimidazoles, hydrogenation
Sodium is dissolved in n,N-Dimethylformamide, is cooled to 0-10 DEG C, is stirred 10-30 minutes, and 1- bromoalkane is added, is warming up to 20-40
DEG C, it stirs 1-5 hours, stops reaction, reaction solution is added in ethyl alcohol, product is precipitated, filter, filter cake is true at 30-70 DEG C
Obtain modified polyphenyl and imidazoles within sky dry 5-15 hours；Wherein polybenzimidazoles, sodium hydride, N,N-dimethylformamide, 1- bromo
The mass ratio of alkane and ethyl alcohol is 12-20：3-7：50-100：5-14：150-200；Wherein the 1- bromoalkane is 1- bromo second
Alkane, 1- n-propyl bromide or 1- bromination of n-butane；
The phenol-formaldehyde resin modified is prepared by following steps：In parts by weight, by phenol, naphthols and formalin
Mixing is added basic catalyst, 70-90 DEG C is warming up under stirring condition, react 4-6 hours, stops heating, use aqueous hydrochloric acid solution
The pH=6-8 of reaction solution is adjusted, reaction solution is cooled to 40-60 DEG C, and vacuum distillation dehydration is cooled to 10-30 DEG C and obtains modified phenolic
Resin；Wherein the mass ratio of phenol, naphthols, formalin and basic catalyst is 100：10-20：100-200：1-2；Described
Basic catalyst is sodium hydroxide, potassium hydroxide, calcium hydroxide or barium hydroxide.
Preferably, basic catalyst is potassium hydroxide.
Preferably, foaming agent is pentane.
Preferably, curing agent is p-methyl benzenesulfonic acid.
It is further preferred that the combined modified phenolic resin foam of a kind of polybenzimidazoles, carboxy nitrile rubber, with parts by weight
Meter, is made of following raw material：55 parts of phenol-formaldehyde resin modified, simultaneously 18 parts of imidazoles of modified polyphenyl, 12 parts of carboxy nitrile rubber, tween-
8010 parts, 11 parts and 10 parts of curing agent of foaming agent.
The invention also includes the preparation sides of a kind of polybenzimidazoles, the combined modified phenolic resin foam of carboxy nitrile rubber
Method includes the following steps：
1. the preparation of modified polyphenyl and imidazoles：In parts by weight, by polybenzimidazoles, sodium hydride is dissolved in N, N- dimethyl methyl
In amide, it is cooled to 0-10 DEG C, is stirred 10-30 minutes, 1- bromoalkane is added, is warming up to 20-40 DEG C, is stirred 1-5 hours, is stopped
Reaction solution is added in ethyl alcohol for reaction, and product is precipitated, and filters, and filter cake is dried in vacuo at 30-70 DEG C 5-15 hours modified
Polybenzimidazoles；Wherein the mass ratio of polybenzimidazoles, sodium hydride, N,N-dimethylformamide, 1- bromoalkane and ethyl alcohol is 12-
20：3-7：50-100：5-14：150-200；Wherein the 1- bromoalkane is 1- bromic ether or 1- n-propyl bromide or 1- bromine
For normal butane；
2. phenol, naphthols and formalin are mixed, basic catalyst is added, is warming up to 70-90 DEG C under stirring condition, instead
It answers 4-6 hours, stops heating, the pH=6-8 of reaction solution is adjusted with aqueous hydrochloric acid solution, reaction solution is cooled to 40-60 DEG C, and vacuum is steamed
Dehydration is evaporated, 10-30 DEG C is cooled to and obtains phenol-formaldehyde resin modified；The wherein mass ratio of phenol, naphthols, formalin and basic catalyst
It is 100：10-20：100-200：1-2；The basic catalyst sodium hydroxide or potassium hydroxide or calcium hydroxide or hydroxide
Barium；
3. by step 2. 50~60 parts of resulting phenol-formaldehyde resin modified, step 1. resulting modified polyphenyl and imidazoles 15-20
Part, 10-15 parts of carboxy nitrile rubber, 8-12 parts of Tween-80,10-12 parts of foaming agent, 5-15 parts of curing agent mixing are warming up to 20-
It 40 DEG C, stirs 20-40 minutes, in the mold of 80-100 DEG C of injection, solidifies 40-80 minutes at 80-100 DEG C, demould to obtain polyphenyl
And the combined modified phenolic resin foam of imidazoles, carboxy nitrile rubber；The foaming agent is pentane or n-hexane or normal heptane
Or petroleum ether；The curing agent is p-methyl benzenesulfonic acid or camphorsulfonic acid.
Preferred preparation method, includes the following steps：
1. the preparation of modified polyphenyl and imidazoles：In parts by weight, by polybenzimidazoles, sodium hydride is dissolved in N, N- dimethyl methyl
In amide, it is cooled to 0-10 DEG C, is stirred 10-30 minutes, 1- n-propyl bromide is added, is warming up to 20-40 DEG C, is stirred 1-5 hours,
Stop reaction, reaction solution is added in ethyl alcohol, product is precipitated, filter, filter cake is dried in vacuo at 30-70 DEG C 5-15 hours
Modified polyphenyl and imidazoles；The wherein mass ratio of polybenzimidazoles, sodium hydride, N,N-dimethylformamide, 1- bromoalkane and ethyl alcohol
It is 15：5：80：10：180；
2. phenol, naphthols and formalin are mixed, basic catalyst is added, 80 DEG C are warming up under stirring condition, reaction
4-6 hours, stopping heating, the pH=7 of reaction solution is adjusted with aqueous hydrochloric acid solution, reaction solution is cooled to 50 DEG C, and vacuum distillation is dehydrated,
It is cooled to 20 DEG C and obtains phenol-formaldehyde resin modified；Wherein the mass ratio of phenol, naphthols, formalin and basic catalyst is 100：15：
180：1.5；The basic catalyst is potassium hydroxide；
3. by step 2. 55 parts of resulting phenol-formaldehyde resin modified, step 1. resulting modified polyphenyl and 18 parts of imidazoles, carboxyl
12 parts of nitrile rubber, 10 parts of Tween-80,11 parts of pentane, 10 parts of p-methyl benzenesulfonic acid mixing are warming up to 30 DEG C, stir 30 minutes,
In the mold of 90 DEG C of injection, solidifies 60 minutes at 90 DEG C, demould to obtain the combined modified phenolic aldehyde of polybenzimidazoles, carboxy nitrile rubber
Resin foam.
The present invention has the following advantages that compared with prior art：
The present invention proposes a kind of polybenzimidazoles, the combined modified phenolic resin foam of carboxy nitrile rubber and its preparation side
Method.Contain naphthols in the phenolic resin starting material that the present invention synthesizes, after naphthols is mixed with phenol, polymerization reaction occurs with formaldehyde, obtains
Rigid planar structure to phenol-formaldehyde resin modified, naphthols can be such that the toughness of phenolic resin and heat resistance greatly improves.Polyphenyl
And imidazoles is a kind of high temperature polymeric materials haveing excellent performance, while having preferable fire retardant performance, can be used as enhancing
Plastics, foamed material etc., the nitrogen-atoms on polybenzimidazoles can form hydrogen bond with the hydroxyl in phenolic resin, to improve
The thermal stability of phenolic resin, the present invention make it more suitable for being blended with phenolic resin by being modified to polybenzimidazoles
It is modified, to improve the performance of phenolic resin.In addition, carboxy nitrile rubber is a kind of traditional phenolic resin toughener, it and it is poly-
Benzimidazole, phenolic resin formed ternary blend systems, available good toughness, high temperature resistant, excellent fireproof performance phenolic aldehyde bubble
Foam.
Specific embodiment
The object of the present invention is to provide a kind of polybenzimidazoles, the combined modified phenolic resin foam of carboxy nitrile rubber, lead to
Cross following technical scheme realization：
A kind of polybenzimidazoles, the combined modified phenolic resin foam of carboxy nitrile rubber, are made of following raw material：Modified phenol
50~60 parts of urea formaldehyde, simultaneously 15-20 parts of imidazoles of modified polyphenyl, 10-15 parts of carboxy nitrile rubber, 8-12 parts of Tween-80, foaming agent
10-12 parts and curing agent 5-15 parts；
The foaming agent is pentane, n-hexane, normal heptane or petroleum ether；
The curing agent is p-methyl benzenesulfonic acid or camphorsulfonic acid；
The modified polyphenyl and imidazoles is prepared by following steps：By polybenzimidazoles, sodium hydride is dissolved in N, N-
In dimethylformamide, it is cooled to 0-10 DEG C, is stirred 10-30 minutes, 1- bromoalkane is added, is warming up to 20-40 DEG C, stirs 1-5
Hour, stop reaction, reaction solution is added in ethyl alcohol, product is precipitated, filters, filter cake is dried in vacuo 5-15 at 30-70 DEG C
Hour obtains modified polyphenyl and imidazoles；Wherein polybenzimidazoles, sodium hydride, N,N-dimethylformamide, 1- bromoalkane and ethyl alcohol
Mass ratio is 12-20：3-7：50-100：5-14：150-200；Wherein the 1- bromoalkane be 1- bromic ether, 1- bromo just
Propane or 1- bromination of n-butane；
The phenol-formaldehyde resin modified is prepared by following steps：Phenol, naphthols and formalin are mixed, alkali is added
Property catalyst, 70-90 DEG C is warming up under stirring condition, is reacted 4-6 hour, heating is stopped, with aqueous hydrochloric acid solution adjusting reaction solution
PH=6-8, reaction solution is cooled to 40-60 DEG C, vacuum distillation dehydration, be cooled to 10-30 DEG C phenol-formaldehyde resin modified；Wherein benzene
Phenol, naphthols, formalin and basic catalyst mass ratio be 100：10-20：100-200：1-2；The basic catalyst
For sodium hydroxide, potassium hydroxide, calcium hydroxide or barium hydroxide.
Preferably, basic catalyst is potassium hydroxide.
Preferably, foaming agent is pentane.
Preferably, curing agent is p-methyl benzenesulfonic acid.
It is further preferred that the combined modified phenolic resin foam of a kind of polybenzimidazoles, carboxy nitrile rubber, by following original
Material composition：55 parts of phenol-formaldehyde resin modified, simultaneously 18 parts of imidazoles of modified polyphenyl, 12 parts of carboxy nitrile rubber, 10 parts of Tween-80, foaming
11 parts and 10 parts of curing agent of agent.
The invention also includes the preparation sides of a kind of polybenzimidazoles, the combined modified phenolic resin foam of carboxy nitrile rubber
Method includes the following steps：
1. the preparation of modified polyphenyl and imidazoles：By polybenzimidazoles, sodium hydride is dissolved in n,N-Dimethylformamide, cooling
It to 0-10 DEG C, stirs 10-30 minutes, 1- bromoalkane is added, be warming up to 20-40 DEG C, stir 1-5 hours, stop reaction, will react
Liquid is added in ethyl alcohol, and product is precipitated, and filters, and filter cake is dried in vacuo to 5-15 hours to obtain modified polyphenyl and imidazoles at 30-70 DEG C；
Wherein the mass ratio of polybenzimidazoles, sodium hydride, N,N-dimethylformamide, 1- bromoalkane and ethyl alcohol is 12-20：3-7：50-
100：5-14：150-200；Wherein the 1- bromoalkane is 1- bromic ether or 1- n-propyl bromide or 1- bromination of n-butane；
2. phenol, naphthols and formalin are mixed, basic catalyst is added, is warming up to 70-90 DEG C under stirring condition, instead
It answers 4-6 hours, stops heating, the pH=6-8 of reaction solution is adjusted with aqueous hydrochloric acid solution, reaction solution is cooled to 40-60 DEG C, and vacuum is steamed
Dehydration is evaporated, 10-30 DEG C is cooled to and obtains phenol-formaldehyde resin modified；The wherein mass ratio of phenol, naphthols, formalin and basic catalyst
It is 100：10-20：100-200：1-2；The basic catalyst sodium hydroxide or potassium hydroxide or calcium hydroxide or hydroxide
Barium；
3. by step 2. 50~60 parts of resulting phenol-formaldehyde resin modified, step 1. resulting modified polyphenyl and imidazoles 15-20
Part, 10-15 parts of carboxy nitrile rubber, 8-12 parts of Tween-80,10-12 parts of foaming agent, 5-15 parts of curing agent mixing are warming up to 20-
It 40 DEG C, stirs 20-40 minutes, in the mold of 80-100 DEG C of injection, solidifies 40-80 minutes at 80-100 DEG C, demould to obtain polyphenyl
And the combined modified phenolic resin foam of imidazoles, carboxy nitrile rubber；The foaming agent is pentane or n-hexane or normal heptane
Or petroleum ether；The curing agent is p-methyl benzenesulfonic acid or camphorsulfonic acid.
Preferred preparation method, includes the following steps：
1. the preparation of modified polyphenyl and imidazoles：By polybenzimidazoles, sodium hydride is dissolved in n,N-Dimethylformamide, cooling
It to 0-10 DEG C, stirs 10-30 minutes, 1- n-propyl bromide is added, be warming up to 20-40 DEG C, stir 1-5 hours, stop reaction, it will
Reaction solution is added in ethyl alcohol, and product is precipitated, and filters, and filter cake is dried in vacuo 5-15 hours at 30-70 DEG C and obtains modified polyphenyl simultaneously
Imidazoles；Wherein the mass ratio of polybenzimidazoles, sodium hydride, N,N-dimethylformamide, 1- bromoalkane and ethyl alcohol is 15：5：80：
10：180；
2. phenol, naphthols and formalin are mixed, basic catalyst is added, 80 DEG C are warming up under stirring condition, reaction
4-6 hours, stopping heating, the pH=7 of reaction solution is adjusted with aqueous hydrochloric acid solution, reaction solution is cooled to 50 DEG C, and vacuum distillation is dehydrated,
It is cooled to 20 DEG C and obtains phenol-formaldehyde resin modified；Wherein the mass ratio of phenol, naphthols, formalin and basic catalyst is 100：15：
180：1.5；The basic catalyst is potassium hydroxide；
3. by step 2. 55 parts of resulting phenol-formaldehyde resin modified, step 1. resulting modified polyphenyl and 18 parts of imidazoles, carboxyl
12 parts of nitrile rubber, 10 parts of Tween-80,11 parts of pentane, 10 parts of p-methyl benzenesulfonic acid mixing are warming up to 30 DEG C, stir 30 minutes,
In the mold of 90 DEG C of injection, solidifies 60 minutes at 90 DEG C, demould to obtain the combined modified phenolic aldehyde of polybenzimidazoles, carboxy nitrile rubber
Resin foam.
Below in conjunction with specific embodiment, the invention will be further described.
Polybenzimidazoles used in the present embodiment is bought in Hubei Xin Kang medication chemistry Co., Ltd；Carboxy nitrile rubber
It buys in Shanghai Li Shenhang International Trading Company Ltd；Tween-80 purchase reaches Chemical Co., Ltd. in Jinan Huifeng.
Embodiment 1
(1) preparation of modified polyphenyl and imidazoles：Polybenzimidazoles 12kg, sodium hydride 3kg are dissolved in 50kgN, N- dimethyl
In formamide, it is cooled to 0 DEG C, is stirred 10 minutes, 1- n-propyl bromide 5kg is added, is warming up to 20 DEG C, is stirred 1 hour, is stopped anti-
It answers, reaction solution is added in 150kg ethyl alcohol, product is precipitated, filter, filter cake is dried in vacuo to be modified within 5 hours at 30 DEG C and is gathered
Benzimidazole；
(2) phenol 100kg, naphthols 10kg and formalin 100kg are mixed, addition potassium hydroxide 1kg, under stirring condition
70 DEG C are warming up to, is reacted 4 hours, heating is stopped, the pH=6 of reaction solution is adjusted with aqueous hydrochloric acid solution, reaction solution is cooled to 40 DEG C,
Vacuum distillation dehydration is cooled to 10 DEG C and obtains phenol-formaldehyde resin modified；
(3) by the resulting phenol-formaldehyde resin modified 50kg of step (2), step (1) resulting modified polyphenyl and imidazoles 15kg, carboxylic
Base nitrile rubber 10kg, Tween-80 8kg, pentane 10kg, p-methyl benzenesulfonic acid 5kg mixing are warming up to 20 DEG C, stir 20 minutes,
In the mold of 80 DEG C of injection, solidifies 40 minutes at 80 DEG C, demould to obtain the combined modified phenolic aldehyde of polybenzimidazoles, carboxy nitrile rubber
Resin foam.
Embodiment 2
(1) preparation of modified polyphenyl and imidazoles：Polybenzimidazoles 15kg, sodium hydride 5kg are dissolved in 80kgN, N- dimethyl
In formamide, 5 DEG C are cooled to, is stirred 20 minutes, 1- n-propyl bromide 10kg is added, is warming up to 30 DEG C, is stirred 3 hours, is stopped
Reaction solution is added in 180kg ethyl alcohol for reaction, and product is precipitated, and filters, and filter cake is dried in vacuo at 50 DEG C 10 hours modified
Polybenzimidazoles；
(2) phenol 100kg, naphthols 15kg and formalin 180kg are mixed, potassium hydroxide 1.5kg, stirring condition is added
Under be warming up to 80 DEG C, react 5 hours, stop heating, the pH=7 of reaction solution is adjusted with aqueous hydrochloric acid solution, reaction solution is cooled to 50
DEG C, vacuum distillation dehydration is cooled to 20 DEG C and obtains phenol-formaldehyde resin modified；
(3) by the resulting phenol-formaldehyde resin modified 55kg of step (2), step (1) resulting modified polyphenyl and imidazoles 18kg, carboxylic
Base nitrile rubber 12kg, Tween-80 10kg, pentane 11kg, p-methyl benzenesulfonic acid 10kg mixing are warming up to 30 DEG C, stir 30 points
Clock in 90 DEG C of mold of injection, solidifies 60 minutes at 90 DEG C, demould polybenzimidazoles, carboxy nitrile rubber are combined modified
Phenolic resin foam.
Embodiment 3
(1) preparation of modified polyphenyl and imidazoles：Polybenzimidazoles 20kg, sodium hydride 7kg are dissolved in 100kgN, N- dimethyl
In formamide, 10 DEG C are cooled to, is stirred 30 minutes, 1- n-propyl bromide 14kg is added, is warming up to 40 DEG C, is stirred 5 hours, is stopped
Reaction solution is added in 200kg ethyl alcohol for reaction, and product is precipitated, and filters, and filter cake is dried in vacuo at 70 DEG C 15 hours modified
Polybenzimidazoles；
(2) phenol 100kg, naphthols 20kg and formalin 200kg are mixed, addition potassium hydroxide 2kg, under stirring condition
90 DEG C are warming up to, is reacted 6 hours, heating is stopped, the pH=8 of reaction solution is adjusted with aqueous hydrochloric acid solution, reaction solution is cooled to 60 DEG C,
Vacuum distillation dehydration is cooled to 30 DEG C and obtains phenol-formaldehyde resin modified；
(3) by the resulting phenol-formaldehyde resin modified 60kg of step (2), step (1) resulting modified polyphenyl and imidazoles 20kg, carboxylic
Base nitrile rubber 15kg, Tween-80 12kg, pentane 12kg, p-methyl benzenesulfonic acid 15kg mixing are warming up to 40 DEG C, stir 40 points
Clock in 100 DEG C of mold of injection, solidifies 80 minutes at 100 DEG C, demould polybenzimidazoles, carboxy nitrile rubber are combined and are changed
Property phenolic resin foam.
Performance test
Bulk density：Its bulk density is measured according to GB6343-1995；
Compression strength：Its compression strength is measured according to GB/T8813-2008；
Oxygen index (OI)：Its oxygen index (OI) is measured according to GB2406-93；
Scaling-off property：Its scaling-off property is measured according to GB/T12812-91.
The performance test knot of polybenzimidazoles obtained by Examples 1 to 3, the combined modified phenolic resin foam of carboxy nitrile rubber
Fruit is shown in Table 1.
Table 1 is the performance of polybenzimidazoles obtained by Examples 1 to 3, the combined modified phenolic resin foam of carboxy nitrile rubber
Test result
| Performance class | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Bulk density | 66kg/m2 | 62kg/m2 | 63kg/m2 |
| Compression strength | 0.61MPa | 0.69MPa | 0.67MPa |
| Oxygen index (OI) | 52% | 55% | 53% |
| Scaling-off property | 3.3% | 3.4% | 3.3% |
As can be seen from Table 1, present invention gained polybenzimidazoles, carboxy nitrile rubber combined modified phenolic resin foam
Bulk density is in 64kg/m2Left and right, compression strength at this time is all in 0.60MPa or more, and scaling-off property is relatively low, this illustrates the phenol
Aldehyde foam compression strength with higher and flexibility；Furthermore the oxygen index (OI) of the phenol formaldehyde foam illustrates that it is same all 50% or more
When have preferable flame retardant property.
Claims (5)
1. the combined modified phenolic resin foam of a kind of polybenzimidazoles, carboxy nitrile rubber, it is characterised in that：In parts by weight,
It is made of following raw material：50~60 parts of phenol-formaldehyde resin modified, simultaneously 15-20 parts of imidazoles of modified polyphenyl, carboxy nitrile rubber 10-15
Part, 8-12 parts of Tween-80,10-12 parts and curing agent 5-15 parts of foaming agent；
The foaming agent is pentane；
The curing agent is p-methyl benzenesulfonic acid；
The modified polyphenyl and imidazoles is prepared by following steps：In parts by weight, by polybenzimidazoles, sodium hydride is molten
In n,N-Dimethylformamide, it is cooled to 0-10 DEG C, is stirred 10-30 minutes, 1- bromoalkane is added, is warming up to 20-40 DEG C, stirs
It mixes 1-5 hours, stops reaction, reaction solution is added in ethyl alcohol, product is precipitated, filter, filter cake is dried in vacuo at 30-70 DEG C
Obtain modified polyphenyl and imidazoles within 5-15 hours；Wherein polybenzimidazoles, sodium hydride, N,N-dimethylformamide, 1- bromoalkane and second
The mass ratio of alcohol is 12-20：3-7：50-100：5-14：150-200；Wherein the 1- bromoalkane is 1- bromic ether, 1- bromine
For n-propane or 1- bromination of n-butane；
The phenol-formaldehyde resin modified is prepared by following steps：In parts by weight, phenol, naphthols and formalin are mixed
It closes, basic catalyst is added, 70-90 DEG C is warming up under stirring condition, reacts 4-6 hours, stops heating, with aqueous hydrochloric acid solution tune
The pH=6-8 of reaction solution is saved, reaction solution is cooled to 40-60 DEG C, and vacuum distillation dehydration is cooled to 10-30 DEG C and obtains modified phenolic resin
Rouge；Wherein the mass ratio of phenol, naphthols, formalin and basic catalyst is 100：10-20：100-200：1-2；The alkali
Property catalyst be sodium hydroxide, potassium hydroxide, calcium hydroxide or barium hydroxide.
2. a kind of polybenzimidazoles according to claim 1, the combined modified phenolic resin foam of carboxy nitrile rubber, special
Sign is：The basic catalyst is potassium hydroxide.
3. a kind of polybenzimidazoles according to claim 1, the combined modified phenolic resin foam of carboxy nitrile rubber, special
Sign is：In parts by weight, it is made of following raw material：55 parts of phenol-formaldehyde resin modified, simultaneously 18 parts of imidazoles of modified polyphenyl, carboxyl butyronitrile
12 parts of rubber, 10 parts of Tween-80,11 parts and 10 parts of curing agent of foaming agent.
4. the preparation side of a kind of polybenzimidazoles described in claim 1, the combined modified phenolic resin foam of carboxy nitrile rubber
Method, it is characterised in that：Include the following steps：
1. the preparation of modified polyphenyl and imidazoles：In parts by weight, by polybenzimidazoles, sodium hydride is dissolved in n,N-Dimethylformamide
In, it is cooled to 0-10 DEG C, is stirred 10-30 minutes, 1- bromoalkane is added, is warming up to 20-40 DEG C, is stirred 1-5 hours, is stopped anti-
It answers, reaction solution is added in ethyl alcohol, product is precipitated, filter, filter cake is dried in vacuo to be modified within 5-15 hours at 30-70 DEG C and is gathered
Benzimidazole；Wherein the mass ratio of polybenzimidazoles, sodium hydride, N,N-dimethylformamide, 1- bromoalkane and ethyl alcohol is 12-
20：3-7：50-100：5-14：150-200；Wherein the 1- bromoalkane is 1- bromic ether or 1- n-propyl bromide or 1- bromine
For normal butane；
2. phenol, naphthols and formalin are mixed, basic catalyst is added, 70-90 DEG C is warming up under stirring condition, reacts 4-
6 hours, stop heating, the pH=6-8 of reaction solution is adjusted with aqueous hydrochloric acid solution, reaction solution is cooled to 40-60 DEG C, and vacuum distillation is de-
Water is cooled to 10-30 DEG C and obtains phenol-formaldehyde resin modified；Wherein the mass ratio of phenol, naphthols, formalin and basic catalyst is
100：10-20：100-200：1-2；The basic catalyst sodium hydroxide or potassium hydroxide or calcium hydroxide or barium hydroxide；
3. by step 2. 50~60 parts of resulting phenol-formaldehyde resin modified, step 1. resulting modified polyphenyl and 15-20 parts of imidazoles, carboxylic
10-15 parts of base nitrile rubber, 8-12 parts of Tween-80,10-12 parts of foaming agent, 5-15 parts of curing agent mixing are warming up to 20-40
DEG C, stir 20-40 minute, inject in 80-100 DEG C of mold, solidify 40-80 minutes at 80-100 DEG C, demould polyphenyl simultaneously
The combined modified phenolic resin foam of imidazoles, carboxy nitrile rubber；The foaming agent is pentane；The curing agent is to first
Benzene sulfonic acid.
5. the system of a kind of polybenzimidazoles according to claim 4, the combined modified phenolic resin foam of carboxy nitrile rubber
Preparation Method, it is characterised in that：Include the following steps：
1. the preparation of modified polyphenyl and imidazoles：In parts by weight, by polybenzimidazoles, sodium hydride is dissolved in n,N-Dimethylformamide
In, it is cooled to 0-10 DEG C, is stirred 10-30 minutes, 1- n-propyl bromide is added, is warming up to 20-40 DEG C, is stirred 1-5 hours, is stopped
Reaction solution is added in ethyl alcohol for reaction, and product is precipitated, and filters, and filter cake is dried in vacuo at 30-70 DEG C 5-15 hours modified
Polybenzimidazoles；Wherein the mass ratio of polybenzimidazoles, sodium hydride, N,N-dimethylformamide, 1- bromoalkane and ethyl alcohol is 15：
5：80：10：180；
2. phenol, naphthols and formalin are mixed, basic catalyst is added, 80 DEG C are warming up under stirring condition, reaction 4-6 is small
When, stop heating, the pH=7 of reaction solution is adjusted with aqueous hydrochloric acid solution, reaction solution is cooled to 50 DEG C, and vacuum distillation is dehydrated, cooling
Phenol-formaldehyde resin modified is obtained to 20 DEG C；Wherein the mass ratio of phenol, naphthols, formalin and basic catalyst is 100：15：180：
1.5；The basic catalyst is potassium hydroxide；
3. by step 2. 55 parts of resulting phenol-formaldehyde resin modified, step 1. resulting modified polyphenyl and 18 parts of imidazoles, carboxyl butyronitrile
12 parts of rubber, 10 parts of Tween-80,11 parts of pentane, 10 parts of p-methyl benzenesulfonic acid mixing are warming up to 30 DEG C, stir 30 minutes, note
Enter in 90 DEG C of mold, solidify 60 minutes at 90 DEG C, demoulds to obtain the combined modified phenolic aldehyde tree of polybenzimidazoles, carboxy nitrile rubber
Fat vacuole foam.
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