CN108384467A - A kind of high-strength anti-flaming adhesive and preparation method thereof - Google Patents
A kind of high-strength anti-flaming adhesive and preparation method thereof Download PDFInfo
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- CN108384467A CN108384467A CN201810114694.XA CN201810114694A CN108384467A CN 108384467 A CN108384467 A CN 108384467A CN 201810114694 A CN201810114694 A CN 201810114694A CN 108384467 A CN108384467 A CN 108384467A
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- flaming
- strength anti
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- unsaturated polyester
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention belongs to adhesive technical fields, and in particular to a kind of high-strength anti-flaming adhesive and preparation method thereof applied on fiberglass；The present invention includes according to the high-strength anti-flaming unsaturated polyester resin of a certain amount of proportioning, cyclohexanone peroxide, cobalt naphthenate, styrene paraffin liquid, octyl dodecanol myristinate, monoglyceride and triethanolamine；Wherein high-strength anti-flaming unsaturated polyester resin acid value is 18mgKOH/g, viscosity 94pa.s, and is especially prepared；The present invention not only high-strength anti-flaming, and adhesive property is very good.
Description
Technical field
The invention belongs to adhesive technical fields, and in particular to a kind of high-strength anti-flaming adhesive applied on fiberglass
And preparation method thereof.
Background technology
Fiberglass scientific name fibre reinforced plastics are commonly called as FRP (Fiber Reinforced Plastics), i.e. fiber reinforcement
Composite plastic.It is divided into glass fiber reinforced composite plastics (GFRP), fibre reinforced composite plastic according to the fiber difference of use
(CFRP), boron fibre enhancing composite plastic etc..It is using glass fibre and its product (glass cloth, band, felt, yarn etc.) as enhancing
Material makees a kind of composite material of basis material with synthetic resin.Fibre reinforced composites are by reinforcing fiber and matrix group
At.The diameter very little of fiber (or whisker), generally at 10 μm hereinafter, defect is less and smaller, breaking strain is about 3/1000ths
It is fragile material within ten, easy damaged, fracture and is corroded.Matrix for fiber, intensity, modulus will it is low very
It is more, but big strain can be withstood, often there is viscoplasticity and elastoplasticity, be toughness material.
Due to its with high-strength light, the excellent performances such as corrosion-resistant, good electrical property, hot property is good, designability is good and
It is applied by wide hair.Since the fiberglass specification of batch production limits, polylith is generally required in practical applications and is spliced；This is just
It needs to use adhesive；But adhesive generally existing used at present cannot take into account transparent and high-strength anti-flaming performance, i.e.,
Just it takes into account, performance is ideal not enough.Adhesive strength is relatively low, and long-time water, which impregnates, is easy cracking.
Invention content
To solve the above-mentioned problems, the purpose of the present invention is to provide a kind of high-strength anti-flaming adhesive, adhesive is not only
It is transparent, and high-strength anti-flaming performance and adhesive strength are all very good.
The second object of the present invention is to provide the preparation method of the high-strength anti-flaming adhesive.
The present invention is achieved through the following technical solutions：
A kind of high-strength anti-flaming adhesive, including the following substance calculated in parts by mass：
Preferably, the cyclohexanone peroxide solution that it is 30%-50% that the cyclohexanone peroxide, which is percent by volume, described
Cobalt naphthenate is the cobalt naphthenate solution that percent by volume is 1%-3%, and the styrene paraffin liquid is that percent by volume is
The styrene paraffin liquor of 0.1%-0.5%.
Preferably, monoglyceride containing saturated fatty acid >=90% in the monoglyceride, iodine number≤4,60 DEG C -70 DEG C of solidification point,
Free acid≤2.5% in terms of stearic acid.
Preferably, the chemical structural formula of the octyl dodecanol myristinate is：
Preferably, the acid value of the high-strength anti-flaming unsaturated polyester resin is 18mgKOH/g, viscosity 94pa.s.
Preferably, the high-strength anti-flaming unsaturated polyester resin includes 5.5 parts of phthalic anhydride, the chlorendic acid calculated in parts by mass
500 parts of 3.0 parts of acid anhydride, 16.5 parts of propylene glycol, 9 parts of epoxychloropropane, 1 part of Dichloroethyl phosphate and styrene are prepared.
The preparation method of the high-strength anti-flaming unsaturated polyester resin：
A. the phthalic anhydride of institute's quantity, chlorendic anhydride, propylene glycol and epoxychloropropane are put into reaction kettle, are passed through inert gas,
Heat temperature raising；
B. when temperature is up to 138 DEG C -142 DEG C, stop heating, keep the temperature 2-3 hours；
C. continue to be heated to 190 DEG C -200 DEG C, when test acidity is 18mgKOH/g, stop heating, keep the temperature 2-3 hours；
D. 75 DEG C are cooled to, the Dichloroethyl phosphate of the amount is added and styrene and is sufficiently stirred, the height is obtained
Intensity flame-retarded unsaturated polyester resin.
Preferably, specific as follows：
A. homogenizer is added in hot water in the octyl dodecanol myristinate of institute's quantity, monoglyceride and triethanolamine
The addition of uniformly obtained mixed solution, the water is octyl dodecanol myristinate, monoglyceride and triethanolamine summation
Twice；
B. by gained mixed solution, high-strength anti-flaming unsaturated polyester resin, cyclohexanone peroxide, aphthenic acids in step A
Cobalt and styrene paraffin liquid are uniformly mixed, and are cured under high-temperature low-pressure, and the high-strength anti-flaming adhesive is made.
Preferably, the hot water that hot water described in step A is 60 DEG C -80 DEG C, mixing speed is 1800 revs/min.
Preferably, described in step B under 0.01-0.1MPa pressure, cure under the conditions of 60 DEG C/12 hours.
The present invention includes high-strength anti-flaming unsaturated polyester resin, cyclohexanone peroxide, aphthenic acids according to a certain ratio
Cobalt, styrene paraffin liquid, octyl dodecanol myristinate, monoglyceride and triethanolamine.Wherein high-strength anti-flaming unsaturation is poly-
Ester resinous acid value is 18mgKOH/g, viscosity 94pa.s, and is especially prepared.The high-strength anti-flaming unsaturated polyester resin is not only
Transparency is good, hard, high-strength flame resistant is good；Especially with cyclohexanone peroxide, cobalt naphthenate, styrene paraffin liquid, octyl
After the additive compatibilities such as lauryl alcohol myristinate, monoglyceride and triethanolamine, excellent water resistance and cohesive force are embodied.
Wherein, cyclohexanone peroxide as initiator can generate free radicals and cause the double bond in unsaturated polyester resin with
Crosslinking agent is copolymerized, is crosslinked and cures.Cobalt naphthenate length is used in combination with peroxyester, but due to its intrinsic certain face
Color and use less；The unsaturated polyester resin prepared in the present invention has high-strength flame resistant but has certain face
Color subsequently with octyl dodecanol myristinate, monoglyceride association reaction, is being transparent, and shear strength is very good.
Specific embodiment
The present invention is described in further detail With reference to embodiment, is managed to help those skilled in the art
The solution present invention.
Embodiment 1
A kind of high-strength anti-flaming adhesive, including the following substance calculated in parts by mass：
90 parts of high-strength anti-flaming unsaturated polyester resin, (35%) 2 part of cyclohexanone peroxide solution, cobalt naphthenate solution
(2%) 2 part, (0.3%) 3 part of styrene paraffin liquid, 1 part of octyl dodecanol myristinate, 1-5 parts of monoglyceride and triethanolamine
2 parts.Wherein, monoglyceride containing saturated fatty acid >=90% in monoglyceride, iodine number≤4,65 DEG C of solidification point are free in terms of stearic acid
Acid≤2.5%.The acid value of high-strength anti-flaming unsaturated polyester resin is 18mgKOH/g, viscosity 94pa.s.
Wherein, the high-strength anti-flaming unsaturated polyester resin includes 5.5 parts of phthalic anhydride, the chlorendic anhydride calculated in parts by mass
500 parts of 3.0 parts, 16.5 parts of propylene glycol, 9 parts of epoxychloropropane, 1 part of Dichloroethyl phosphate and styrene are prepared.
The preparation method of its high-strength anti-flaming unsaturated polyester resin：
A. the phthalic anhydride of institute's quantity, chlorendic anhydride, propylene glycol and epoxychloropropane are put into reaction kettle, are passed through inert gas,
Heat temperature raising；
B. when temperature is up to 140 DEG C, stop heating, keep the temperature 2.5 hours；
C. continue to be heated to 195 DEG C, when test acidity is 18mgKOH/g, stop heating, keep the temperature 2.5 hours；
D. 75 DEG C are cooled to, the Dichloroethyl phosphate of the amount is added and styrene and is sufficiently stirred, the height is obtained
Intensity flame-retarded unsaturated polyester resin.
A kind of preparation method of high-strength anti-flaming adhesive：
A. in hot water high speed is added for (70 DEG C) in the octyl dodecanol myristinate of institute's quantity, monoglyceride and triethanolamine
Mixed solution (mixing speed is 1800 revs/min) is uniformly made in blender, and the addition of the water is octyl dodecanol nutmeg
Twice of acid esters, monoglyceride and triethanolamine summation；
B. by gained mixed solution, high-strength anti-flaming unsaturated polyester resin, cyclohexanone peroxide, aphthenic acids in step A
Cobalt and styrene paraffin liquid are uniformly mixed, and are cured under the conditions of lower 60 DEG C/12 hours in high-temperature low-pressure (0.05MPa), are made described
High-strength anti-flaming adhesive.
Embodiment 2
A kind of high-strength anti-flaming adhesive, including the following substance calculated in parts by mass：
82 parts of high-strength anti-flaming unsaturated polyester resin, (30%) 5 part of cyclohexanone peroxide solution, cobalt naphthenate solution
(1%) 5 part, (0.1%) 5 part of styrene paraffin liquid, 1 part of octyl dodecanol myristinate, 1 part of monoglyceride and triethanolamine 1
Part.Wherein, monoglyceride containing saturated fatty acid >=90% in monoglyceride, iodine number≤4,60 DEG C of solidification point are free in terms of stearic acid
Acid≤2.5%.The acid value of high-strength anti-flaming unsaturated polyester resin is 18mgKOH/g, viscosity 94pa.s.
Wherein, the high-strength anti-flaming unsaturated polyester resin includes 5.5 parts of phthalic anhydride, the chlorendic anhydride calculated in parts by mass
500 parts of 3.0 parts, 16.5 parts of propylene glycol, 9 parts of epoxychloropropane, 1 part of Dichloroethyl phosphate and styrene are prepared.
The preparation method of its high-strength anti-flaming unsaturated polyester resin：
A. the phthalic anhydride of institute's quantity, chlorendic anhydride, propylene glycol and epoxychloropropane are put into reaction kettle, are passed through inert gas,
Heat temperature raising；
B. when temperature is up to 138 DEG C, stop heating, keep the temperature 2 hours；
C. continue to be heated to 190 DEG C, when test acidity is 18mgKOH/g, stop heating, keep the temperature 2 hours；
D. 75 DEG C are cooled to, the Dichloroethyl phosphate of the amount is added and styrene and is sufficiently stirred, the height is obtained
Intensity flame-retarded unsaturated polyester resin.
A kind of preparation method of high-strength anti-flaming adhesive：
A. in hot water high speed is added for (60 DEG C) in the octyl dodecanol myristinate of institute's quantity, monoglyceride and triethanolamine
Mixed solution (mixing speed is 1800 revs/min) is uniformly made in blender, and the addition of the water is octyl dodecanol nutmeg
Twice of acid esters, monoglyceride and triethanolamine summation；
B. by gained mixed solution, high-strength anti-flaming unsaturated polyester resin, cyclohexanone peroxide, aphthenic acids in step A
Cobalt and styrene paraffin liquid are uniformly mixed, and are cured under the conditions of lower 60 DEG C/12 hours in high-temperature low-pressure (0.01MPa), are made described
High-strength anti-flaming adhesive.
Embodiment 3
A kind of high-strength anti-flaming adhesive, including the following substance calculated in parts by mass：
94 parts of high-strength anti-flaming unsaturated polyester resin, (50%) 1 part of cyclohexanone peroxide solution, cobalt naphthenate solution
(3%) 1 part, (0.5%) 1 part of styrene paraffin liquid, 1 part of octyl dodecanol myristinate, 1 part of monoglyceride and triethanolamine 1
Part.Wherein, monoglyceride containing saturated fatty acid >=90% in monoglyceride, iodine number≤4,70 DEG C of solidification point are free in terms of stearic acid
Acid≤2.5%.The acid value of high-strength anti-flaming unsaturated polyester resin is 18mgKOH/g, viscosity 0.18/pa.s.
Wherein, the high-strength anti-flaming unsaturated polyester resin includes 5.5 parts of phthalic anhydride, the chlorendic anhydride calculated in parts by mass
500 parts of 3.0 parts, 16.5 parts of propylene glycol, 9 parts of epoxychloropropane, 1 part of Dichloroethyl phosphate and styrene are prepared.
The preparation method of its high-strength anti-flaming unsaturated polyester resin：
A. the phthalic anhydride of institute's quantity, chlorendic anhydride, propylene glycol and epoxychloropropane are put into reaction kettle, are passed through inert gas,
Heat temperature raising；
B. when temperature is up to 142 DEG C, stop heating, keep the temperature 3 hours；
C. continue to be heated to 200 DEG C, when test acidity is 18mgKOH/g, stop heating, keep the temperature 3 hours；
D. 75 DEG C are cooled to, the Dichloroethyl phosphate of the amount is added and styrene and is sufficiently stirred, the height is obtained
Intensity flame-retarded unsaturated polyester resin.
A kind of preparation method of high-strength anti-flaming adhesive：
A. the octyl dodecanol myristinate of institute's quantity, monoglyceride and triethanolamine are added for (60 DEG C -80 DEG C) in hot water
Enter homogenizer and mixed solution (mixing speed is 1800 revs/min) is uniformly made, the addition of the water is octyl dodecanol
Twice of myristinate, monoglyceride and triethanolamine summation；
B. by gained mixed solution, high-strength anti-flaming unsaturated polyester resin, cyclohexanone peroxide, aphthenic acids in step A
Cobalt and styrene paraffin liquid are uniformly mixed, and are cured under the conditions of lower 60 DEG C/12 hours in high-temperature low-pressure (0.01-0.1MPa), are made
The high-strength anti-flaming adhesive.
Above-described embodiment, only presently preferred embodiments of the present invention, is not used for limiting the scope of the present invention, therefore all with this
The equivalent change or modification that feature and principle described in invention claim are done, should all be included in scope of the invention as claimed
Within.
Experimental comparison：
307 traditional unsaturated polyester cross-linking agent are compared with the present invention, performance comparison result such as refers to table 1：
Wherein comparative example 1：307 unsaturated polyester cross-linking agent, comparative example 2：Inventive formulation, but it is free from octyl dodecanol
Myristinate, comparative example 3：Inventive formulation, but it is free from monoglyceride.
High-strength anti-flaming is tested, and heat safe fiberglass is chosen in experiment.
Table 1
As can be seen from Table 1, the high-strength anti-flaming adhesive of the present invention is for bonding aluminium, organic glass and polystyrene, it is stretched
There is no too big advantages for intensity and shear strength relative contrast example 1, but it is used for the bonding of fiberglass, tensile strength and cut
Shearing stress is far longer than comparative example 1,2,3, illustrates that monoglyceride and octyl dodecanol myristinate combination and unsaturated polyester (UP) are logical
It crosses after method of the present invention is prepared, cohesive force greatly improves, and it is with fire-retardant, low cigarette, low toxicity and high-strength
Performance.
Claims (10)
1. a kind of high-strength anti-flaming adhesive, it is characterised in that：Including the following substance calculated in parts by mass：
The wherein described high-strength anti-flaming unsaturated polyester resin is by phthalic anhydride, chlorendic anhydride, propylene glycol, epoxychloropropane, two chloroethenes
Base phosphate and styrene are prepared.
2. high-strength anti-flaming adhesive as described in claim 1, it is characterised in that：The cyclohexanone peroxide is percent by volume
For the cyclohexanone peroxide solution of 30%-50%, the cobalt naphthenate is that the cobalt naphthenate that percent by volume is 1%-3% is molten
Liquid, the styrene paraffin liquid are the styrene paraffin liquor that percent by volume is 0.1%-0.5%.
3. high-strength anti-flaming adhesive as described in claim 1, it is characterised in that：List containing saturated fatty acid is sweet in the monoglyceride
Ester >=90%, iodine number≤4,60 DEG C -70 DEG C of solidification point, free acid≤2.5% in terms of stearic acid.
4. high-strength anti-flaming adhesive as described in claim 1, it is characterised in that：The change of the octyl dodecanol myristinate
Learning structural formula is：
5. high-strength anti-flaming adhesive as described in claim 1, it is characterised in that：The high-strength anti-flaming unsaturated polyester resin
Acid value be 18mgKOH/g, viscosity 94pa.s.
6. high-strength anti-flaming adhesive as claimed in claim 5, it is characterised in that：The high-strength anti-flaming unsaturated polyester resin
Including 3.0 parts of 5.5 parts of phthalic anhydride, chlorendic anhydride, 16.5 parts of propylene glycol, 9 parts of epoxychloropropane, the Dichloroethyl calculated in parts by mass
500 parts of 1 part of phosphate and styrene are prepared.
7. high-strength anti-flaming adhesive as claimed in claim 6, it is characterised in that：The high-strength anti-flaming unsaturated polyester resin
Preparation method：
A. the phthalic anhydride of institute's quantity, chlorendic anhydride, propylene glycol and epoxychloropropane are put into reaction kettle, are passed through inert gas, heated
Heating；
B. when temperature is up to 138 DEG C -142 DEG C, stop heating, keep the temperature 2-3 hours；
C. continue to be heated to 190 DEG C -200 DEG C, when test acidity is 18mgKOH/g, stop heating, keep the temperature 2-3 hours；
D. 75 DEG C are cooled to, the Dichloroethyl phosphate of the amount is added and styrene and is sufficiently stirred, the high intensity is obtained
Flame-retarded unsaturated polyester resin.
8. the preparation method of any one of the claim 1-7 high-strength anti-flaming adhesive, which is characterized in that specifically such as
Under：
A. it is uniform homogenizer to be added in hot water in the octyl dodecanol myristinate of institute's quantity, monoglyceride and triethanolamine
Be made mixed solution, the addition of the hot water be octyl dodecanol myristinate, monoglyceride and triethanolamine summation two
Times；
B. by step A gained mixed solution, high-strength anti-flaming unsaturated polyester resin, cyclohexanone peroxide, cobalt naphthenate and
Styrene paraffin liquid is uniformly mixed, and is cured under high-temperature low-pressure, and the high-strength anti-flaming adhesive is made.
9. high-strength anti-flaming adhesive as claimed in claim 8, it is characterised in that：Hot water described in step A is 60 DEG C -80 DEG C
Hot water, mixing speed are 1800 revs/min.
10. high-strength anti-flaming adhesive as claimed in claim 8, it is characterised in that：It is pressed in 0.01-0.1MPa described in step B
Under power, cure under the conditions of 60 DEG C/12 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810114694.XA CN108384467A (en) | 2018-02-06 | 2018-02-06 | A kind of high-strength anti-flaming adhesive and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810114694.XA CN108384467A (en) | 2018-02-06 | 2018-02-06 | A kind of high-strength anti-flaming adhesive and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN108384467A true CN108384467A (en) | 2018-08-10 |
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ID=63075157
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810114694.XA Withdrawn CN108384467A (en) | 2018-02-06 | 2018-02-06 | A kind of high-strength anti-flaming adhesive and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112223450A (en) * | 2020-11-02 | 2021-01-15 | 石家庄华杰木业有限公司 | Surface flame-retardant artificial board |
-
2018
- 2018-02-06 CN CN201810114694.XA patent/CN108384467A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112223450A (en) * | 2020-11-02 | 2021-01-15 | 石家庄华杰木业有限公司 | Surface flame-retardant artificial board |
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Application publication date: 20180810 |