CN109897322A - A kind of low-density Flame retardant solid buoyancy material and preparation method - Google Patents
A kind of low-density Flame retardant solid buoyancy material and preparation method Download PDFInfo
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- CN109897322A CN109897322A CN201910170735.1A CN201910170735A CN109897322A CN 109897322 A CN109897322 A CN 109897322A CN 201910170735 A CN201910170735 A CN 201910170735A CN 109897322 A CN109897322 A CN 109897322A
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Abstract
The present invention relates to solid buoyancy material technical fields, and a kind of low-density Flame retardant solid buoyancy material and preparation method are disclosed, which includes the raw material of following parts by weight proportion: 14.4-24 parts of methacrylonitriles, 15.2-25.4 parts of methacrylic acids, 0.2-0.4 parts of azodiisobutyronitriles, 2 parts of tert-butyl alcohols, 2.8 parts of allyl methacrylates, 5-15 parts of melamine condensed phosphates, 1-2 parts of polyvinyl alcohol, 1.3 parts of resorcinols bis- (diphenyl phosphoesters), 7-12 parts of epoxy resin, 1.8 parts of isophorone diamine.The present invention solves Flame retardant solid buoyancy material in the prior art, while realizing effectively fire-retardant, cannot achieve the technical issues of its own weight is effectively reduced.
Description
Technical field
The present invention relates to solid buoyancy material technical field, specially a kind of low-density Flame retardant solid buoyancy material and preparation
Method.
Background technique
In recent years, solid buoyancy material has been widely used in marine drilling platform, oil exploitation marine riser and underwater
The ocean development equipment such as the latent device of operation.As exploration and development of the mankind to ocean is more and more deep, to solid buoyancy material
Demand it is also increasing, it is followed by that the fields such as the equipment of use and storage solid buoyancy material, ship and storage
Fire risk also greatly increase.Fire in order to prevent reduces the loss of fire bring, develop it is a kind of itself have it is fire-retardant
The solid buoyancy material of property becomes extremely important.
The patent of invention that Authorization Notice No. is CN102775727B discloses a kind of Flame retardant solid buoyancy material and its preparation
Method, however its added fire retardant is halogen containing flame-retardant, this makes material in the production and use process, can give environment band
Carry out certain pollution, is unfavorable for the use of marine environment.
Authorization Notice No. discloses a kind of halogen-free flameproof solid buoyancy material for the patent of invention of CN103865236B, however
Poly- phosphamide flame-proof modifier therein causes polycondensation reaction by surface, is grafted on hollow glass micropearl surface, this
Although method can prepare the superior solid buoyancy material of flame retardant effect, poly- phosphamide flame-proof modifier is in solid buoyancy material
In content be up to 5~30%, this will seriously increase the density of solid buoyancy material.
The present invention provides a kind of low-density Flame retardant solid buoyancy material and preparation method, it is intended to solve fire-retardant in the prior art
Solid buoyancy material cannot achieve the technical issues of its own weight is effectively reduced while realizing effectively fire-retardant.
Summary of the invention
(1) the technical issues of solving
In view of the deficiencies of the prior art, the present invention provides a kind of low-density Flame retardant solid buoyancy material and preparation method,
It solves Flame retardant solid buoyancy material in the prior art, while realizing effectively fire-retardant, cannot achieve and its own is effectively reduced
The technical issues of weight.
(2) technical solution
To achieve the above object, the invention provides the following technical scheme:
A kind of low-density Flame retardant solid buoyancy material, the raw material including following parts by weight proportion: 14.4-24 parts of methyl
Acrylonitrile, 15.2-25.4 part methacrylic acid, 0.2-0.4 parts of azodiisobutyronitriles, 2 parts of tert-butyl alcohols, 2.8 parts of methacrylic acids
Allyl ester, 5-15 parts of melamine condensed phosphates, 1-2 parts of polyvinyl alcohol, 1.3 parts of resorcinols bis- (diphenyl phosphoesters),
7-12 parts of epoxy resin, 1.8 parts of isophorone diamine.
Preferably, the raw material including following parts by weight proportion: 25mL methacrylonitrile, 20mL methacrylic acid, 0.4g
Azodiisobutyronitrile, the 5g tert-butyl alcohol, 3mL allyl methacrylate, 8g melamine condensed phosphate, 2g polyvinyl alcohol, 1mL
Resorcinol bis- (diphenyl phosphoesters), 10g epoxy resin, 2mL isophorone diamine.
Preferably, the epoxy resin is E03 trade mark bisphenol A type epoxy resin.
Preferably, the viscosity of the polyvinyl alcohol is 50.
A kind of preparation method of low-density Flame retardant solid buoyancy material, comprising the following steps:
It S1. is original with methacrylonitrile, methacrylic acid, azodiisobutyronitrile, the tert-butyl alcohol, allyl methacrylate
Material, preparation obtain matrix component；
S2. by step S1 matrix component and 5-15 parts of melamine condensed phosphates, 1-2 parts of polyvinyl alcohol and distillation
Water is injected after mixing in the mold of sealing, is placed in 60-80 DEG C of water-bath, and constant temperature polymerization reaction 24-36h is demoulded later,
At 150-200 DEG C, foamable reaction is carried out, component A is prepared；
S3. with E03 trade mark bisphenol A type epoxy resin, butanone, isophorone diamine, the bis- (diphenylphosphoric acids of resorcinol
Ester) it is raw material, adhesion component is prepared；
S4. the component A in step S2 is added in the adhesion component in step S3, stirs evenly, is placed in vacuum oven
Interior middle vacuum evacuation bubble, is prepared solid buoyancy material.
Preferably, in the step S2, after foamable reaction, it is cooled to 100-140 DEG C, reacts 2h at 100-140 DEG C.
(3) beneficial technical effect
Compared with prior art, the present invention have it is following the utility model has the advantages that
After tested, the oxygen index (OI) for the solid buoyancy material that the present invention prepares is 32.2-35.9, density 0.24-
0.33g/cm3；
Oxygen index (OI) 28.2, density 0.64g/cm with the solid buoyancy material prepared in comparative example of the present invention3It compares, this
The solid buoyancy material of invention improves oxygen index (OI) not only significantly, and it is significant reduce autologous density, thus realizing
While effectively fire-retardant, the technical effect that its own weight is effectively reduced is achieved.
Specific embodiment
Embodiment one:
Solid buoyancy material includes following raw material: 25mL methacrylonitrile (ρ 0.8g/cm3), 20mL methacrylic acid
(ρ 1.015g/cm3), 0.4g azodiisobutyronitrile, the 5g tert-butyl alcohol, 3mL allyl methacrylate (ρ 0.94g/cm3)、8g
Melamine condensed phosphate, 2g polyvinyl alcohol (viscosity 50), 10mL distilled water, the bis- (diphenylphosphoric acids of 1mL resorcinol
Ester) (ρ 1.317g/cm3), 10gE03 trade mark bisphenol A type epoxy resin, 20mL butanone (ρ 0.805g/cm3), the different Buddhist of 2mL
You are ketone diamines (ρ 0.924g/cm3)；
The preparation method of above-mentioned solid buoyancy material the following steps are included:
S1. 25mL methacrylonitrile, 20mL methacrylic acid, 0.4g azodiisobutyronitrile, the 5g tert-butyl alcohol, 3mL methyl are taken
Allyl acrylate, preparation obtain matrix component；
S2. by the matrix component and 8g melamine condensed phosphate, 2g polyvinyl alcohol, 10mL distilled water in step S1
It injects in the mold of sealing, is placed in 80 DEG C of water-bath after mixing, constant temperature polymerization reaction 30h is demoulded, later by copolymer
It is placed in the baking oven that preheating temperature is 105 DEG C, with the heating rate of 5 DEG C/min, is warming up to 200 DEG C, the foamable reaction at 200 DEG C
2h is cooled to 140 DEG C later, reacts 3h at 140 DEG C, is cooled to room temperature, component A is prepared；
S3. first 10gE03 trade mark bisphenol A type epoxy resin is dissolved in 20mL butanone, adds 2mL isophorone two
Amine and 1mL resorcinol are bis- (diphenyl phosphoester), stir evenly, adhesion component is prepared；
S4. the component A in step S2 is added in the adhesion component in step S3, stirs evenly, is placed in vacuum oven
60min is steeped in interior middle vacuum evacuation, and solid buoyancy material is prepared；
S5. combustion testing-oxygen index (OI) method of testing specified in GB2406, the solid buoyancy material in testing procedure S4 are used
Oxygen index (OI) be 35.9, while the density of the solid buoyancy material in testing procedure S4 be 0.27g/cm3；
Wherein, oxygen index (OI) refers under the defined conditions, and material carries out needed for flaming combustion in oxygen-nitrogen mixed gas stream
Minimum oxygen concentration, oxygen index (OI) is higher, and expression material is more nonflammable, i.e., flame retardant property is better.It is generally acknowledged that oxygen index (OI) < 22 belong to
Combustible material, oxygen index (OI) belong to combustible material between 22~27, and oxygen index (OI) > 27 belong to nonflammable material.
Embodiment two:
Solid buoyancy material includes following raw material: 30mL methacrylonitrile, 25mL methacrylic acid, 0.3g azo two are different
Butyronitrile, the 2g tert-butyl alcohol, 3mL allyl methacrylate, 15g melamine condensed phosphate, 1g polyvinyl alcohol, 10mL distillation
Water, 1mL resorcinol bis- (diphenyl phosphoesters), 12gE03 trade mark bisphenol A type epoxy resin, 20mL butanone, 2mL isophorone
Diamines；
The preparation method of above-mentioned solid buoyancy material the following steps are included:
S1. 30mL methacrylonitrile, 25mL methacrylic acid, 0.3g azodiisobutyronitrile, the 2g tert-butyl alcohol, 3mL methyl are taken
Allyl acrylate, preparation obtain matrix component；
S2. by the matrix component and 15g melamine condensed phosphate, 1g polyvinyl alcohol, 10mL distilled water in step S1
It injects in the mold of sealing, is placed in 70 DEG C of water-bath after mixing, constant temperature polymerization reaction for 24 hours, demoulds later, by copolymer
It is placed in the baking oven that preheating temperature is 80 DEG C, with the heating rate of 5 DEG C/min, is warming up to 180 DEG C, the foamable reaction at 180 DEG C
2h is cooled to 120 DEG C later, reacts 3h at 120 DEG C, is cooled to room temperature, component A is prepared；
S3. first 12gE03 trade mark bisphenol A type epoxy resin is dissolved in 20mL butanone, adds 2mL isophorone two
Amine and 1mL resorcinol are bis- (diphenyl phosphoester), stir evenly, adhesion component is prepared；
S4. the component A in step S2 is added in the adhesion component in step S3, stirs evenly, is placed in vacuum oven
60min is steeped in interior middle vacuum evacuation, and solid buoyancy material is prepared；
S5. combustion testing-oxygen index (OI) method of testing specified in GB2406, the solid buoyancy material in testing procedure S4 are used
Oxygen index (OI) be 35.1, while the density of the solid buoyancy material in testing procedure S4 be 0.24g/cm3。
Embodiment three:
Solid buoyancy material includes following raw material: 18mL methacrylonitrile, 15mL methacrylic acid, 0.2g azo two are different
Butyronitrile, the 2g tert-butyl alcohol, 3mL allyl methacrylate, 5g melamine condensed phosphate, 2g polyvinyl alcohol, 10mL distillation
Water, 1mL resorcinol bis- (diphenyl phosphoesters), 7gE03 trade mark bisphenol A type epoxy resin, 20mL butanone, 2mL isophorone
Diamines；
The preparation method of above-mentioned solid buoyancy material the following steps are included:
S1. 18mL methacrylonitrile, 15mL methacrylic acid, 0.2g azodiisobutyronitrile, the 2g tert-butyl alcohol, 3mL methyl are taken
Allyl acrylate, preparation obtain matrix component；
S2. by the matrix component and 5g melamine condensed phosphate, 2g polyvinyl alcohol, 10mL distilled water in step S1
It injects in the mold of sealing, is placed in 60 DEG C of water-bath after mixing, constant temperature polymerization reaction 36h is demoulded, later by copolymer
It is placed in the baking oven that preheating temperature is 80 DEG C, with the heating rate of 5 DEG C/min, is warming up to 150 DEG C, the foamable reaction at 150 DEG C
2h is cooled to 100 DEG C later, reacts 3h at 100 DEG C, is cooled to room temperature, component A is prepared；
S3. first 7gE03 trade mark bisphenol A type epoxy resin is dissolved in 20mL butanone, adds 2mL isophorone two
Amine and 1mL resorcinol are bis- (diphenyl phosphoester), stir evenly, adhesion component is prepared；
S4. the component A in step S2 is added in the adhesion component in step S3, stirs evenly, is placed in vacuum oven
90min is steeped in interior middle vacuum evacuation, and solid buoyancy material is prepared；
S5. combustion testing-oxygen index (OI) method of testing specified in GB2406, the solid buoyancy material in testing procedure S4 are used
Oxygen index (OI) be 32.2, while the density of the solid buoyancy material in testing procedure S4 be 0.33g/cm3。
Comparative example:
Solid buoyancy material includes following raw material: 25mL methacrylonitrile, 20mL methacrylic acid, 0.4g azo two are different
Butyronitrile, the 5g tert-butyl alcohol, 3mL allyl methacrylate, 2g melamine condensed phosphate；
The preparation method of above-mentioned solid buoyancy material the following steps are included:
S1. 25mL methacrylonitrile, 20mL methacrylic acid, 0.4g azodiisobutyronitrile, the 5g tert-butyl alcohol, 3mL methyl are taken
Allyl acrylate, preparation obtain matrix component；
S2., matrix component in step S1 is injected to the mold of sealing after mixing with 8g melamine condensed phosphate
In, it is placed in 80 DEG C of water-bath, constant temperature polymerization reaction 30h is demoulded later, and copolymer is placed in the baking that preheating temperature is 105 DEG C
In case, with the heating rate of 5 DEG C/min, 200 DEG C are warming up to, the foamable reaction 2h at 200 DEG C is cooled to 140 DEG C later, in
3h is reacted at 140 DEG C, is cooled to room temperature, component A is prepared；
S3. the component A in step S2 is placed in middle vacuum evacuation in vacuum oven and steeps 60min, it is floating that solid is prepared
Dead-wood material；
S4. combustion testing-oxygen index (OI) method of testing specified in GB2406, the solid buoyancy material in testing procedure S3 are used
Oxygen index (OI) be 28.2, while the density of the solid buoyancy material in testing procedure S3 be 0.64g/cm3。
Claims (6)
1. a kind of low-density Flame retardant solid buoyancy material, which is characterized in that the raw material including following parts by weight proportion: 14.4-
24 parts of methacrylonitriles, 15.2-25.4 parts of methacrylic acids, 0.2-0.4 parts of azodiisobutyronitriles, 2 parts of tert-butyl alcohols, 2.8 parts of first
Base allyl acrylate, 5-15 parts of melamine condensed phosphates, 1-2 parts of polyvinyl alcohol, 1.3 parts of bis- (diphenyl of resorcinol
Phosphate), 7-12 parts of epoxy resin, 1.8 parts of isophorone diamine.
2. solid buoyancy material according to claim 1, which is characterized in that the raw material including following parts by weight proportion:
25mL methacrylonitrile, 20mL methacrylic acid, 0.4g azodiisobutyronitrile, the 5g tert-butyl alcohol, 3mL allyl methacrylate,
8g melamine condensed phosphate, 2g polyvinyl alcohol, 1mL resorcinol bis- (diphenyl phosphoesters), 10g epoxy resin, 2mL are different
Isophoronediamine.
3. solid buoyancy material according to claim 1 or 2, which is characterized in that the epoxy resin is E03 trade mark bis-phenol
A type epoxy resin.
4. solid buoyancy material according to claim 1, which is characterized in that the viscosity of the polyvinyl alcohol is 50.
5. a kind of preparation method of low-density Flame retardant solid buoyancy material, which comprises the following steps:
S1. using methacrylonitrile, methacrylic acid, azodiisobutyronitrile, the tert-butyl alcohol, allyl methacrylate as raw material, match
Matrix component is made；
S2. the matrix component in step S1 is mixed with 5-15 parts of melamine condensed phosphates, 1-2 parts of polyvinyl alcohol and distilled water
After closing uniformly in the mold of injection sealing, it is placed in 60-80 DEG C of water-bath, constant temperature polymerization reaction 24-36h is demoulded later, in
At 150-200 DEG C, foamable reaction is carried out, component A is prepared；
S3. it is with E03 trade mark bisphenol A type epoxy resin, butanone, isophorone diamine, resorcinol bis- (diphenyl phosphoesters)
Adhesion component is prepared in raw material；
S4. the component A in step S2 is added in the adhesion component in step S3, is stirred evenly, is placed in vacuum oven
Vacuum evacuation bubble, is prepared solid buoyancy material.
6. preparation method according to claim 5, which is characterized in that in the step S2, after foamable reaction, be cooled to
100-140 DEG C, 2h is reacted at 100-140 DEG C.
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| CN103421206A (en) * | 2013-07-24 | 2013-12-04 | 江苏科技大学 | Preparation method for acrylonitrile/methacrylic acid copolymer foamed plastic |
| CN103865236A (en) * | 2014-02-13 | 2014-06-18 | 甘肃康博丝特新材料有限责任公司 | Halogen-free flame retardant solid buoyancy material and preparation method thereof |
| CN106432592A (en) * | 2016-09-19 | 2017-02-22 | 浙江中科恒泰新材料科技有限公司 | Preparation method for improving polymethacrylimide foam processing yield |
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2019
- 2019-03-07 CN CN201910170735.1A patent/CN109897322A/en not_active Withdrawn
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5229886A (en) * | 1975-09-01 | 1977-03-07 | Mitsubishi Rayon Co Ltd | Process for producing flame-retarded acrylonitrile copolymers |
| CN101709130A (en) * | 2009-11-19 | 2010-05-19 | 海洋化工研究院 | Ultra-low density solid buoyant material and manufacture method |
| CN102775727A (en) * | 2011-05-09 | 2012-11-14 | 海洋化工研究院 | Flame retardant solid buoyancy material and preparation method thereof |
| CN102432971A (en) * | 2011-09-14 | 2012-05-02 | 刘天义 | Methylpropylene imine foam plastic and preparation process thereof |
| CN103421206A (en) * | 2013-07-24 | 2013-12-04 | 江苏科技大学 | Preparation method for acrylonitrile/methacrylic acid copolymer foamed plastic |
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