CN107759749A - Reaction-type flame-retarding vinyl ester resin of synergy and preparation method thereof - Google Patents
Reaction-type flame-retarding vinyl ester resin of synergy and preparation method thereof Download PDFInfo
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- CN107759749A CN107759749A CN201711022407.4A CN201711022407A CN107759749A CN 107759749 A CN107759749 A CN 107759749A CN 201711022407 A CN201711022407 A CN 201711022407A CN 107759749 A CN107759749 A CN 107759749A
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- vinyl ester
- ester resin
- retarding
- reaction
- flame
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1466—Acrylic or methacrylic acids
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1488—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing phosphorus
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Emergency Medicine (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to reaction-type flame-retarding vinyl ester resin of synergy and preparation method thereof, belong to vinyl ester resin technical field.It is prepared by materials such as epoxy resin, response type phosphonium flame retardant, unsaturated monoacid, catalyst, polymerization inhibitor and crosslinkable monomers through series reaction.The present invention is by the way that response type phosphorus and the bromine and nitrogen that can be acted on conjunction with which are introduced into vinyl ester resin, drastically increase flame retarding efficiency, response type vinyl ester resin in the case of identical addition compared to traditional additive flame retardant and single-element has flame retarding efficiency height, stable performance, the characteristics of addition is low, it can be applied in the field higher to fire resistance requirement；In addition, this resin viscosity is moderate, have good workability, a variety of operating procedures such as hand paste, injection, roller coat can be widely used in；The corrosion-resistant of vinyl ester resin, heat resistance and high tenacity and the high flame resistance of reaction-type flame-retarding are had concurrently.
Description
Technical field
The present invention relates to vinyl ester resin technical field, the reaction-type flame-retarding vinyl of more particularly to a kind of synergy
Ester resin and preparation method thereof.
Background technology
Vinyl ester resin is progressively obtained in industry-by-industry by development in the last few years and is widely applied.It is logical
It is often prepared by carrying out esterification by ring opening reaction by unsaturated organic mono carboxylic acid and epoxy, using made of vinyl ester resin
Composite generally has excellent mechanics and resistance to elevated temperatures, and decay resistance.It is multiple under more fierce market competition
The manufacturer of condensation material also proposes higher requirement to the security performance of material, and compound made of vinyl ester resin
Material is respectively provided with combustibility, oxygen index (OI) easy firing typically under 20 or so, atmospheric environment.Thus, it is higher for flame-retardancy requirements
Product, it is necessary to carry out the flame-retardant modified of matrix resin, could meet the needs of product.It is single in the fire resistance of lifting resin
The fire retardation of one element often has its limit, but often multielement synergy can cause the fire resistance of resin at double
Raising because different ignition-proof elements often corresponds to different fire retardant mechanisms, during a variety of ignition-proof elements synergies
Mean that a variety of fire retardant mechanisms while act on material in itself, promote mutually, play the effect that one-plus-one is more than two.
In general, it is flame-retardant modified to resin progress to have two methods, one：Fire retardant is added in matrix material, such as
Aluminium hydroxide, ammonium polyphosphate, triethyl group phosphorus chloride (TCEP) etc..Chinese patent literature CN104693691A, which discloses one kind, to be made
The method being used in conjunction with ammonium polyphosphate and carbon forming agent improves the method for resins fire retardant performance, is had using resin made of this method
Higher oxygen index (OI), smoke density and cigarette poison are relatively low, but the usage amount of additive flame retardant is larger, and can not produce and have to printing opacity
It is required that product.Secondly：Reactive flame retardant is added in the building-up process of matrix resin, improves the anti-flammability of matrix resin
Energy.Chinese patent literature CN103641961A discloses one kind and uses phosphoric acid as reactive flame retardant to improve resins fire retardant
Can method, this method cost is cheap, can improve the fire resistance of vinyl ester resin, but the addition pair of single ignition-proof element
The lifting of fire resistance is limited, and raw material of the phosphoric acid as three-functionality-degree, and activity is extremely strong, participates in putting during reaction
Popular drama is strong, it is difficult to controls, and also the molecular resin amount synthesized is big, and viscosity is bigger than normal, and operability is poor, and complex operation is cumbersome.
Chinese patent literature CN104031213B disclose a kind of low smoke and zero halogen heat-resistant fireproof vinyl ester resin and its
Preparation method, product corresponding to the invention is primarily directed to two performances of high temperature resistant and halogen-free flameproof, product shows white pasty state
Liquid.Product flame-proof ethylene base ester resin corresponding to the invention has that flame retarding efficiency is low, and addition is high, and operability is poor, and performance is not
A series of problems, such as stable.
In view of this, it is very intentional to develop a kind of flame-proof ethylene base ester resin of the multielement synergy of high-efficient simple
Justice.
The content of the invention
The purpose of the present invention is the defects of overcoming prior art to exist, there is provided one kind solves existing flame-proof ethylene base ester tree
The reaction-type flame-retarding second of the synergy for a series of problems, such as fat flame retarding efficiency is low, and addition is high, and operability is poor, and performance is unstable
Alkenyl esters resin and preparation method thereof.
Realizing the technical scheme of the object of the invention is：A kind of reaction-type flame-retarding vinyl ester resin of synergy, including
The each component of following mass percent：
The mass percent summation of each component is 100%.
Above-mentioned technical proposal has each component of following mass percent：
Epoxy resin described in above-mentioned technical proposal is bisphenol type epoxy and and brominated bisphenol A epoxy resin.
Catalyst described in above-mentioned technical proposal is tetramethyl ammonium chloride, triethanolamine, benzyl dimethylamine, benzyl triethyl ammonium chlorine
Change one kind in ammonium, N, accelerine, triphenyl phosphorus.
Unsaturated monocarboxylic acid described in above-mentioned technical proposal is one kind in methacrylic acid, acrylic acid, butenoic acid.
Polymerization inhibitor described in above-mentioned technical proposal be quinhydrones, methylnaphthohydroquinone, 2,2,6,6- tetramethyl -4- hydroxy piperidine nitrogen oxygen from
By one kind in base (TMHP0), phenthazine.
Response type phosphonium flame retardant described in above-mentioned technical proposal is the miscellaneous -10- phospho hetero phenanthrenes -10- oxidations of 9,10- dihydro-9-oxies
One kind in thing (DOPO), phosphorous acid, diethyl phosphite.
Crosslinkable monomers described in above-mentioned technical proposal are by one kind in styrene, methyl methacrylate and N- ethene
Base pyrrolidones forms.
Raw material A, B, C are put into reactor by above-mentioned technical proposal, at 120~150 DEG C, react 2~3 hours, then
D, E are added, at 120~130 DEG C, reacts 2~4 hours, addition F, G high-speed stirred is uniform after being down to room temperature, closed preservation.
After adopting the above technical scheme, the present invention has following positive effect：
(1) present invention uses brominated epoxy part substitute commonly be free of ignition-proof element epoxy, its main purpose be
The halogen with flame retardant effect is introduced in resin, and is incorporated in the form of response type in resin, increases the fire resistance of resin,
And contrast the advantage that the brominated flame-retarded resin of tradition has flame retarding efficiency high and anti-aging anti-yellowing property is good.
(2) polymerization inhibitor used in the present invention, catalyst have passed through layer by layer preferably, shorten the reaction time, improve production
Efficiency, and possess longer storage stability, it is ensured that the stability of product.
(3) present invention is made up of the relatively low raw material of price, and it is low to prepare cost；Acted synergistically with reference to a variety of ignition-proof elements, it is fire-retardant
Effect is better than in the market like product；The flame-proof ethylene base ester resin for the synergy that the technique productions come out has high fire-retardance
Property, corrosion-resistant, high temperature resistant, the production available for construction material, automotive part etc..
(4) all ignition-proof elements of the invention are attached in resin in a manner of response type, and dosage is few, efficiency high；Should
Flame-retarded resin viscosity is low, has good workability, simple to operate, expands a variety of behaviour such as construction means, hand paste, roller coat, injection
Make technique；The high flame retardant of the corrosion-resistant of vinyl ester resin, high temperature resistant, high tenacity and Flame Retardant Unsaturated Polyester Resin is had concurrently
Can, it is widely used, especially suitable for the product being had higher requirements with fire resistance corrosion-resistant to product such as anode tube, plane skylight
Making；The loading of filler can be greatly reduced as matrix resin in high fire-retardance filler resin system, is solved
High fire-retardance resin will generally fill the problem of mass filler.
(5) present invention by response type phosphorus and the bromine that can be acted on conjunction with which and nitrogen by introducing vinyl esters tree
In fat, flame retarding efficiency is drastically increased, compared to traditional additive flame retardant and single-element in the case of identical addition
Response type vinyl ester resin have that flame retarding efficiency is high, stable performance, the characteristics of addition is low, can be applied to anti-flammability
Energy is required in higher field.
Embodiment
(embodiment 1)
Each component is weighed by following quality：
By raw material A, B, C input reactor, at 140 DEG C, 2 hours are reacted, then add D, E, at 120 DEG C, instead
2 hours are answered, addition F, G high-speed stirred is uniform after being down to room temperature, closed preservation.
(embodiment 2)
Each component is weighed by following quality：
By raw material A, B, C input reactor, at 120 DEG C, 2.5 hours are reacted, then add D, E, at 125 DEG C,
2 hours are reacted, addition F, G high-speed stirred is uniform after being down to room temperature, closed preservation.
(embodiment 3)
Each component is weighed by following quality：
By raw material A, B, C input reactor, at 110 DEG C, 3 hours are reacted, then add D, E, at 105 DEG C, instead
4 hours are answered, addition F, G high-speed stirred is uniform after being down to room temperature, closed preservation.
(embodiment 4)
Each component is weighed by following quality：
By raw material A, B, C input reactor, at 115 DEG C, 3 hours are reacted, then add D, E, at 110 DEG C, instead
3.5 hours are answered, addition F, G high-speed stirred is uniform after being down to room temperature, closed preservation.
(embodiment 5)
Each component is weighed by following quality：
By raw material A, B, C input reactor, at 140 DEG C, 2 hours are reacted, then add D, E, at 120 DEG C, instead
2 hours are answered, addition F, G high-speed stirred is uniform after being down to room temperature, closed preservation.
(embodiment 6)
Each component is weighed by following quality：
By raw material A, B, C input reactor, at 110 DEG C, 2 hours are reacted, then add D, E, at 105 DEG C, instead
2 hours are answered, addition F, G high-speed stirred is uniform after being down to room temperature, closed preservation.
(comparative example 1)
Each component is weighed by following quality：
By raw material A, B input reactors, at 140 DEG C, 2 hours are reacted, then add C, D, at 120 DEG C, reaction 2
Individual hour, addition E, F high-speed stirred is uniform after being down to room temperature, closed preservation.
(comparative example 2)
Each component is weighed by following quality：
By raw material A, B, C, D input reactor, at 120 DEG C, 4 hours are reacted, E, F high-speed stirring are added after being down to room temperature
Mix uniformly, closed preservation.
Pour mass, firming body is made according to standard GB/T/T2567-2008 in the flame-retarded resin that various embodiments above obtains
System：Accelerator 0.6%/Naph2%, curing agent AKZO M-50 2%, the processing of fiberglass solidify afterwards：Room temperature × 24h+80 DEG C ×
2h+120℃×3h。
Two comparative examples, the only reactive pattern phosphorus fire retardant of comparative example 1 are made referring concurrently to prior art, comparative example 2 only has
Response type bromine flame retardant, is made glass fiber reinforced plastics product as described above.
Table 1：The data of mechanical of embodiment and comparative example
High flame resistance is primarily directed in the present invention, while having had certain resistance to elevated temperatures concurrently.Due to second
Ene based resins in itself have good resistance to elevated temperatures thus the present invention in not using phenolic resin come further enhance tree
The resistance to elevated temperatures of fat, but relatively inexpensive conventional epoxies E44 and E51 are have selected, it is a certain degree of resistance to remaining
Cost is reduced on the basis of high-temperature behavior.
In addition, anti-flammability can also be increased to a certain extent by substituting non-flame resistant class epoxy using brominated epoxy part in the present invention
Energy.In the selection of main reactive flame retardant, in addition to more general DOPO, the present invention is investigated and its structure class
As the effect of diethyl phosphite and phosphorous acid as reactive flame retardant, as a result confirm to have and similar contain P-H bond structures
Such material can be used under the system of vinylite as reactive flame retardant.
Thus, in the use of reactive flame retardant, the present invention proposes selection more more diversified than documents.
In the selection of crosslinkable monomers, the present invention in documents compared to NVP is added, and the material is as friendship
While receipts or other documents in duplicate body, system viscosity can be reduced and play synergy with P the and Br elements in resin, add the resistance of product
Fire performance.
Substantial amounts of filler is added in documents CN104031213B as additive flame retardant, this results in final
Product can decline without transparent and overall physical property, for the multifarious consideration in products application direction, the present invention
In and be not added with such material so that the final products in the present invention both can apply to the industrial product for having demand to the transparency
Such as plane skylight, in can also being applied to have the industrial product of high requirement to anti-flammability after supplement adds filler, as track is handed over
Logical inside gadget.
The present invention and the documents CN104031213B main distinction：
For from the appearance, the present invention is yellow transparent liquid, is white paste liquid in documents；
For from physical property, product flexibility of the invention is stronger, and rigidity is slightly poor, is mainly reflected in fracture elongation and modulus
On；
The present invention is comprehensively better than the product in documents in fire resistance, is mainly reflected in oxygen index (OI)；
The present invention is suitable with documents in resistance to elevated temperatures, is mainly reflected in heat distortion temperature；
Following data embody in the form of fiberglass comes, and fiberglass is made according to standard GB/T/T8237 in fiberglass,
Lamination structure is 9 layer of 0.4 alkali-free woven roving, cure system：Accelerator 0.6%/Naph2%, curing agent AKZO M-50 2%.
The processing of fiberglass solidify afterwards：100℃×3h+150℃×1h.2 DEG C of characteristics are as follows：
Particular embodiments described above, the purpose of the present invention, technical scheme and beneficial effect are carried out further in detail
Describe in detail it is bright, should be understood that the foregoing is only the present invention specific embodiment, be not intended to limit the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution and improvements done etc., it should be included in the guarantor of the present invention
Within the scope of shield.
Claims (9)
- A kind of 1. reaction-type flame-retarding vinyl ester resin of synergy, it is characterised in that：Including each of following mass percent Component：The mass percent summation of each component is 100%.
- 2. the reaction-type flame-retarding vinyl ester resin of synergy according to claim 1, it is characterised in that：With following The each component of mass percent：
- 3. the reaction-type flame-retarding vinyl ester resin of synergy according to claim 1 or 2, it is characterised in that：It is described Epoxy resin for bisphenol type epoxy and and brominated bisphenol A epoxy resin.
- 4. the reaction-type flame-retarding vinyl ester resin of synergy according to claim 1 or 2, it is characterised in that：It is described Catalyst is tetramethyl ammonium chloride, triethanolamine, benzyl dimethylamine, benzyltriethylammoinium chloride, N, accelerine, triphen One kind in base phosphorus.
- 5. the reaction-type flame-retarding vinyl ester resin of synergy according to claim 1 or 2, it is characterised in that：It is described Unsaturated monocarboxylic acid is one kind in methacrylic acid, acrylic acid, butenoic acid.
- 6. the reaction-type flame-retarding vinyl ester resin of synergy according to claim 1 or 2, it is characterised in that：It is described Polymerization inhibitor is one kind in quinhydrones, methylnaphthohydroquinone, 2,2,6,6- tetramethyl -4- hydroxy piperidines NO free radical, phenthazine.
- 7. the reaction-type flame-retarding vinyl ester resin of synergy according to claim 1 or 2, it is characterised in that：It is described Response type phosphonium flame retardant is in 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phosphorous acid, diethyl phosphite One kind.
- 8. the reaction-type flame-retarding vinyl ester resin of synergy according to claim 1 or 2, it is characterised in that：It is described Crosslinkable monomers are made up of one kind in styrene, methyl methacrylate and NVP.
- 9. a kind of preparation method of the reaction-type flame-retarding vinyl ester resin of synergy as described in claim 1 to 8 is any, It is characterized in that：By raw material A, B, C input reactor, at 120~150 DEG C, 2~3 hours are reacted, then add D, E, At 120~130 DEG C, 2~4 hours are reacted, addition F, G high-speed stirred is uniform after being down to room temperature, closed preservation.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711022407.4A CN107759749A (en) | 2017-10-27 | 2017-10-27 | Reaction-type flame-retarding vinyl ester resin of synergy and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711022407.4A CN107759749A (en) | 2017-10-27 | 2017-10-27 | Reaction-type flame-retarding vinyl ester resin of synergy and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111995755A (en) * | 2020-08-24 | 2020-11-27 | 浙江晨诺高分子材料有限公司 | Vinyl ester flame-retardant resin containing polyester structure and preparation method thereof |
| CN113024790A (en) * | 2021-02-04 | 2021-06-25 | 东莞市德聚胶接技术有限公司 | Intrinsic flame-retardant acrylate oligomer and acrylate structural adhesive |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6291626B1 (en) * | 1998-06-19 | 2001-09-18 | National Science Council | Phosphorus-containing dihydric phenol or naphthol-advanced epoxy resin or cured |
| CN104031213A (en) * | 2014-05-30 | 2014-09-10 | 常州华科聚合物股份有限公司 | Low-smoke halogen-free high-temperature-resistant flame-retardant vinyl ester resin and preparation method thereof |
| CN105017729A (en) * | 2015-08-21 | 2015-11-04 | 永悦科技股份有限公司 | Synthetic method of efficient flame-retardant epoxy vinyl ester resin |
| CN105175994A (en) * | 2015-08-03 | 2015-12-23 | 广东生益科技股份有限公司 | Epoxy resin composition for copper-clad plate and application thereof |
-
2017
- 2017-10-27 CN CN201711022407.4A patent/CN107759749A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6291626B1 (en) * | 1998-06-19 | 2001-09-18 | National Science Council | Phosphorus-containing dihydric phenol or naphthol-advanced epoxy resin or cured |
| CN104031213A (en) * | 2014-05-30 | 2014-09-10 | 常州华科聚合物股份有限公司 | Low-smoke halogen-free high-temperature-resistant flame-retardant vinyl ester resin and preparation method thereof |
| CN105175994A (en) * | 2015-08-03 | 2015-12-23 | 广东生益科技股份有限公司 | Epoxy resin composition for copper-clad plate and application thereof |
| CN105017729A (en) * | 2015-08-21 | 2015-11-04 | 永悦科技股份有限公司 | Synthetic method of efficient flame-retardant epoxy vinyl ester resin |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111995755A (en) * | 2020-08-24 | 2020-11-27 | 浙江晨诺高分子材料有限公司 | Vinyl ester flame-retardant resin containing polyester structure and preparation method thereof |
| CN113024790A (en) * | 2021-02-04 | 2021-06-25 | 东莞市德聚胶接技术有限公司 | Intrinsic flame-retardant acrylate oligomer and acrylate structural adhesive |
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