CN106543646A - A kind of poly- alkyl hypophosphites and phosphate compounds synergistic fire retarding epoxide resin and preparation method thereof - Google Patents
A kind of poly- alkyl hypophosphites and phosphate compounds synergistic fire retarding epoxide resin and preparation method thereof Download PDFInfo
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- CN106543646A CN106543646A CN201610936730.1A CN201610936730A CN106543646A CN 106543646 A CN106543646 A CN 106543646A CN 201610936730 A CN201610936730 A CN 201610936730A CN 106543646 A CN106543646 A CN 106543646A
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- phosphate compounds
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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
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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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
- C08L2201/22—Halogen free composition
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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- Fireproofing Substances (AREA)
Abstract
The present invention relates to a kind of poly- alkyl hypophosphites and phosphate compounds synergistic fire retarding epoxide resin, its preparation method is by poly- alkyl hypophosphites and phosphate compounds are carried out melt blending at a certain temperature with bisphenolA-glycidol ether epoxy resin, organic solvent, firming agent are added thereto to again, the curing reaction of epoxy resin is completed at a certain temperature, obtains the epoxy resin cured product of excellent fireproof performance;Fire retardant only need to be mixed homogeneously by way of stirring by the method with epoxy resin, it is not necessary to carry out chemical bonding reaction between the two, simple;The ethoxyline resin antiflaming excellent performance that compounding is obtained, the limited oxygen index of epoxy resin cured product can reach 35.0%, and fire-retardant rank can reach 0 grade of UL94V, can be used as electrical and electronic component material.
Description
Technical field
The present invention relates to a kind of new poly- alkyl hypophosphites and phosphate compounds compound and made by fire-retardant ring
Oxygen tree fat and preparation method thereof, belongs to the preparing technical field of fire retarding epoxide resin, especially adds in ordinary epoxy resin
Specific flame-retardant composition obtains flame-retardant epoxide resin material.
Background technology
Epoxy resin is the thermosetting that a class has good adhesion, electrical insulating property, chemical resistance and low-shrinkage
Macromolecular material, has a wide range of applications in electronic enterprises, Aero-Space, transportation and military domain;But,
Easily be ignited without fire-retardant epoxy resin, limited oxygen index (LOI) relatively low (about 19.8), and can drip after igniting be difficult to from
Put out;Life, property and the public security for giving people brings very big hidden danger, therefore needs in actual use to carry out epoxy resin
It is flame-retardant modified, to reduce the generation of such disaster.
Alkyl phosphinate is the new generation of green environmental protection phosphorus flame retardant developed in recent years, and its general molecular formula is (R2POO)
N-Mn+, R therein are C1-C6Alkyl, M is metal;The features such as which has stability height, water-tolerant, high flame retarding efficiency, makees
Develop for a kind of phosphorus series non-halogen flame retardant very rapid;Phosphate compounds are very rapid in developed recently, and which is in engineering
Application in terms of plastics and thermosetting resin constantly extends, and of home make phosphate flame retardant quality is similar with foreign countries at present
Product quality is suitable;According to report at present and the Patents announced and research paper, by alkyl phosphinate and phospha
When phenanthrene is applied in epoxy resin, both can play synergism, so as to obtain higher flame retarding efficiency.
The present invention adopts poly- alkyl hypophosphites (especially poly- hexyl hypo-aluminum orthophosphate (APHP)) and phosphate compounds
The flame-retardant system for being constituted, is not reported in the proprietary material of current document and oneself announcement.
The content of the invention
Present invention aims to the deficiencies in the prior art, there is provided a kind of poly- alkyl hypophosphites and phosphoric acid ester
Compound fire retarding epoxide resin and preparation method thereof, by poly- alkyl hypophosphites and phosphate compounds are contracted with bisphenol-A two
Water glycerin ether epoxy resin carries out melt blending at a certain temperature, and adds organic solvent and firming agent, carries out curing reaction
Prepared fire retarding epoxide resin solidfied material.
The poly- alkyl hypophosphites of the present invention and the preparation method of phosphate compounds synergistic fire retarding epoxide resin, including
Following steps:
1) bisphenolA-glycidol ether epoxy resin is heated, under agitation by poly- alkyl hypophosphites and phosphoric acid
Ester type compound is added in above-mentioned epoxy resin;
2) by step 1) process after epoxy resin cooling, add organic solvent under agitation, mix the two equal
It is even;
3) firming agent is added to into step 2) in the epoxy-resin systems that obtain, after stirring, take out in vacuum drying oven
Vacuum, then poured in mould, heating makes organic solvent volatilize and carry out epoxy resin cure reaction, obtains poly- alkyl
Phosphate and phosphate compounds synergistic fire retarding epoxide resin.
In above-mentioned technical proposal, it is preferred that the poly- alkyl hypophosphites for adopting are poly- hexyl hypo-aluminum orthophosphate (APHP) (purity
It is prepared by > 97%, laboratory), its chemical structural formula is:
Preferably, described phosphate compounds can be double (diphenyl) phosphate ester (BDP) (purity > of bisphenol-A
98%, technical grade), resorcinol double (diphenyl) phosphate ester (RDP) (purity > 98%, technical grade), dimethyl methyl phosphonates
(DMMP) (purity > 98%, technical grade), triphenyl phosphate (TPP) (purity > 98%, technical grade), tricresyl phosphate (chloro isopropyl)
One or more in ester (TCPP) (purity > 98%, technical grade);
Preferably, the epoxide number of described bisphenolA-glycidol ether epoxy resin is generally in the range of 0.10-0.54.
(DGEBA, technical grade)
Preferably, described organic solvent is usually acetone (purity > 98%, technical grade), butanone (purity > 98%, work
Industry level), pentanone (purity > 98%, technical grade), one or more in methyl iso-butyl ketone (MIBK) (purity > 98%, technical grade).
Preferably, described firming agent can be 4,4 '-DADPS (DDS) (purity > 98%, technical grade), 4,
4 '-MDA (DDM) (purity > 98%, technical grade), linear phenolic resin (PN) (technical grade), m-diaminobenzene.
(mPDA) one kind in (purity > 98%, technical grade).
Preferably, the preparation side of described poly- alkyl hypophosphites and phosphate compounds synergistic fire retarding epoxide resin
Method, its concrete steps can be as follows:
1) bisphenolA-glycidol ether epoxy resin is heated to into 50-180 DEG C, under agitation by poly- alkyl time phosphorus
Hydrochlorate and phosphate compounds are added in above-mentioned epoxy resin, the poly- alkyl hypophosphites for being added and phosphoric acid ester chemical combination
2%-40% of the mixture quality of thing for bisphenolA-glycidol ether epoxy resin, mixing time are 0.2-2.0 hours;
2) by step 1) process after epoxy resin be cooled to 30-120 DEG C, add organic solvent under agitation, make
The two mix homogeneously;The quality of the organic solvent for being added is step 1) 0%-90% of material gross mass that obtains, during stirring
Between be 0.2-2.0 hours;
3) firming agent being added to into step 2) in the epoxy-resin systems that obtain, the quality of added firming agent is bisphenol-A
The 5%-50% of diglycidyl ether epoxy resin quality, after stirring, the evacuation in vacuum drying oven, then poured in
In mould, being heated to 50-200 DEG C makes organic solvent volatilize and carries out epoxy resin cure reaction 1-20 hours, obtains poly- alkyl
Hypophosphites and phosphate compounds synergistic fire retarding epoxide resin.
Adopt the poly- alkyl hypophosphites and phosphate compounds synergistic flame retardant epoxy tree for preparing with the aforedescribed process
Fat.
Fire retarding epoxide resin is prepared using said method, only fire retardant need to be mixed with epoxy resin by way of stirring
Uniformly, it is not necessary to carry out chemical bonding reaction between the two, it is simple;Additionally, adopting APHP and phosphate compounds multiple
The ethoxyline resin antiflaming excellent performance matched somebody with somebody, when firming agent is that the mass fraction of DDS, APHP and BDP in system is 10%, addition
Ratio is 1:When 2, the limited oxygen index of epoxy resin cured product reaches 35.0%, and fire-retardant rank can reach UL94V-0 levels;
1 firming agent of table is the fire resistance of the part epoxy solidfied material that DDS fire retardant mass fractions are 8%
It is 1 that 2 firming agent of table is DDS adding proportions:The fire resistance of 2 part epoxy solidfied material
Specific embodiment
Embodiment 1
The bisphenolA-glycidol ether epoxy resin that 100g epoxide numbers are 0.51 is heated to into 180 DEG C, under agitation
4.8g APHP and 9.8g BDP are added in above-mentioned epoxy resin, after stirring 30 minutes, 120 DEG C is cooled to, then by 31.7g
DDS is added in epoxy resin, the gas after stirring under vacuum in removing system, then is poured into prior preheating
In mould, first precuring 3 hours at 150 DEG C, then solidification 5 hours at 180 DEG C obtain fire retarding epoxide resin, the asphalt mixtures modified by epoxy resin
In fat solidfied material, the mass fraction of fire retardant is 10%, and limited oxygen index is 35.0%.
Embodiment 2
The bisphenolA-glycidol ether epoxy resin that 100g epoxide numbers are 0.51 is heated to into 180 DEG C, under agitation
5.0g APHP and 12.0g BDP are added in epoxy resin, after stirring 1 hour, system 75 DEG C is cooled to into, to asphalt mixtures modified by epoxy resin
60mL butanone is added in fat and is stirred 1 hour, 31.7g DDS are added in epoxy resin, in vacuum condition after stirring
Organic solvent in lower removing system, then be poured in the mould of prior preheating, first precuring 3 hours at 150 DEG C, then
Solidify 5 hours at 180 DEG C, obtain fire retarding epoxide resin, limited oxygen index is 33.7%.
Embodiment 3
The bisphenolA-glycidol ether epoxy resin that 100g epoxide numbers are 0.51 is heated to into 120 DEG C, under agitation
2.4g APHP and 7.2g BDP are added in epoxy resin, after stirring 1 hour, 25.3g DDM epoxy resin is added to into
In, then the gas after stirring under vacuum in removing system is poured in the mould of prior preheating, first 120
Precuring 2 hours at DEG C, then solidify 4 hours at 150 DEG C, obtain fire retarding epoxide resin.
Embodiment 4
The bisphenolA-glycidol ether epoxy resin that 100g epoxide numbers are 0.51 is heated to into 120 DEG C, under agitation
5.3g APHP and 2.7g BDP are added in epoxy resin, after stirring 1 hour, system 75 DEG C is cooled to into, to epoxy resin
Middle addition 60mL butanone is simultaneously stirred 1 hour, 25.3g DDM is added in epoxy resin, after stirring under vacuum
Organic solvent in removing system, then be poured in the mould of prior preheating, first precuring 2 hours at 120 DEG C, then 150
Solidify 5 hours at DEG C, obtain fire retarding epoxide resin.
Embodiment 5
The bisphenolA-glycidol ether epoxy resin that 100g epoxide numbers are 0.46 is heated to into 180 DEG C, under agitation
6.2g APHP and 2.7g BDP are added in epoxy resin, are stirred 1.5 hours, system is cooled to into 80 DEG C;To epoxy resin
Middle addition 50mL pentanones are simultaneously stirred 1 hour, 29.8g PN are added in epoxy resin, are taken off after stirring under vacuum
Except the organic solvent in system, then it is poured in the mould of prior preheating, first precuring 3 hours at 150 DEG C, then at 180 DEG C
Lower solidification 5 hours, obtains fire retarding epoxide resin.
Embodiment 6
The bisphenolA-glycidol ether epoxy resin that 100g epoxide numbers are 0.44 is heated to into 180 DEG C, under agitation
8.5g APHP and 2.8g RDP are added in epoxy resin, after stirring 1 hour, 12.4g mPDA epoxy resin is added to into
In, the gas after stirring under vacuum in removing system, then be poured in the mould of prior preheating, first at 150 DEG C
Lower precuring 3 hours, then solidify 5 hours at 180 DEG C, obtain fire retarding epoxide resin.
The preferred embodiments of the present invention are the foregoing is only, the present invention is not limited to, for the skill of this area
For art personnel, the present invention can have various modifications and variations;It is all within the spirit and principles in the present invention, made any repair
Change, equivalent, improvement etc., should be included within the scope of the present invention.
Claims (8)
1. the preparation method of a kind of poly- alkyl hypophosphites and phosphate compounds synergistic fire retarding epoxide resin, its feature exist
In comprising the steps:
1) bisphenolA-glycidol ether epoxy resin is heated, under agitation by poly- alkyl hypophosphites and phosphoric acid ester
Compound is added in above-mentioned epoxy resin;
2) by step 1) process after epoxy resin cooling, add organic solvent under agitation, make the two mix homogeneously;
3) firming agent is added to into step 2) in the epoxy-resin systems that obtain, after stirring, the evacuation in vacuum drying oven,
Poured in mould again, heating makes organic solvent volatilize and carry out epoxy resin cure reaction, obtains poly- alkyl hypophosphorous acid
Salt and phosphate compounds synergistic fire retarding epoxide resin.
2. the preparation of poly- alkyl hypophosphites according to claim 1 and phosphate compounds synergistic fire retarding epoxide resin
Method, it is characterised in that the poly- alkyl hypophosphites for adopting are poly- hexyl hypo-aluminum orthophosphate (APHP), its chemical structural formula is:
3. the preparation of poly- alkyl hypophosphites according to claim 1 and phosphate compounds synergistic fire retarding epoxide resin
Method, it is characterised in that described phosphate compounds are double (diphenyl) phosphate esters (BDP) of bisphenol-A, resorcinol pair
(diphenyl) phosphate ester (RDP), dimethyl methyl phosphonate (DMMP), triphenyl phosphate (TPP), tricresyl phosphate (chloro isopropyl) ester
(TCPP) one or more in.
4. the preparation of poly- alkyl hypophosphites according to claim 1 and phosphate compounds synergistic fire retarding epoxide resin
Method, it is characterised in that the epoxide number scope of described bisphenolA-glycidol ether epoxy resin is 0.10-0.54.
5. the preparation of poly- alkyl hypophosphites according to claim 1 and phosphate compounds synergistic fire retarding epoxide resin
Method, it is characterised in that described organic solvent is acetone, butanone, pentanone, one or more in methyl iso-butyl ketone (MIBK).
6. the preparation of poly- alkyl hypophosphites according to claim 1 and phosphate compounds synergistic fire retarding epoxide resin
Method, it is characterised in that described firming agent is 4,4 '-DADPS, 4,4 '-MDA, novolac
One kind in resin, m-diaminobenzene..
7. the preparation of poly- alkyl hypophosphites according to claim 1 and phosphate compounds synergistic fire retarding epoxide resin
Method, it is characterised in that
1) bisphenolA-glycidol ether epoxy resin is heated to into 50-180 DEG C, under agitation by APHP and phosphoric acid ester
Compound is added in above-mentioned epoxy resin, and the APHP for being added and the mixture quality of phosphate compounds are bisphenol-A two
The 2%-40% of tetraglycidel ether epoxy resin, and APHP and phosphate compounds mass ratio are 1:10-10:1, mixing time
For 0.2-2.0 hours;
2) by step 1) process after epoxy resin be cooled to 30-120 DEG C, add organic solvent under agitation, make the two
Mix homogeneously;The quality of the organic solvent for being added is step 1) 0%-90% of material gross mass that obtains, mixing time is
0.2-2.0 hours;
3) firming agent being added to into step 2) in the epoxy-resin systems that obtain, the quality of added firming agent contracts for bisphenol-A two
The 5%-50% of water glycerin ether epoxy resin quality, after stirring, the evacuation in vacuum drying oven, then poured in mould
In, being heated to 50-200 DEG C makes organic solvent volatilize and carries out epoxy resin cure reaction 1-20 hours, obtains poly- alkyl time phosphorus
Hydrochlorate and phosphate compounds synergistic fire retarding epoxide resin.
8. the poly- alkyl hypophosphites for being prepared using the method as described in any one of claim 1-7 and phosphoric acid ester chemical combination
Thing synergistic fire retarding epoxide resin.
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109370172A (en) * | 2018-10-26 | 2019-02-22 | 北京科方创业科技企业孵化器有限公司 | A kind of halogen-free flameproof PET material and preparation method thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101633770A (en) * | 2009-08-28 | 2010-01-27 | 番禺南沙殷田化工有限公司 | Halogen-free flame retardant epoxy resin composite and flexible copper clad laminate prepared with same |
CN102993641A (en) * | 2012-08-22 | 2013-03-27 | 常熟市筑紫机械有限公司 | Preparation method of halogen-free flame retardant phenolic epoxy glass reinforced plastic molding material |
CN104311712A (en) * | 2014-08-26 | 2015-01-28 | 北京工商大学 | Preparation method for polyalkyl hypophosphite |
-
2016
- 2016-10-25 CN CN201610936730.1A patent/CN106543646B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101633770A (en) * | 2009-08-28 | 2010-01-27 | 番禺南沙殷田化工有限公司 | Halogen-free flame retardant epoxy resin composite and flexible copper clad laminate prepared with same |
CN102993641A (en) * | 2012-08-22 | 2013-03-27 | 常熟市筑紫机械有限公司 | Preparation method of halogen-free flame retardant phenolic epoxy glass reinforced plastic molding material |
CN104311712A (en) * | 2014-08-26 | 2015-01-28 | 北京工商大学 | Preparation method for polyalkyl hypophosphite |
Non-Patent Citations (3)
Title |
---|
JINGYU WANG ET AL: "Synergistic flame-retardant behavior and mechanisms of aluminum poly-hexamethylenephosphinate and phosphaphenanthrene in epoxy resin", 《POLYMER DEGRADATION AND STABILITY》 * |
刘益军编著: "《聚氨酯原料及助剂手册》", 31 January 2013 * |
耿星编著: "《现代水性涂料助剂手册》", 30 June 2007 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109370172A (en) * | 2018-10-26 | 2019-02-22 | 北京科方创业科技企业孵化器有限公司 | A kind of halogen-free flameproof PET material and preparation method thereof |
CN109370172B (en) * | 2018-10-26 | 2021-09-14 | 北京科方创业科技企业孵化器有限公司 | Halogen-free flame-retardant PET material and preparation method thereof |
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