CN103497349B - A kind of pre-cured fiberglass cloth impregnant and preparation method thereof - Google Patents
A kind of pre-cured fiberglass cloth impregnant and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of pre-cured fiberglass cloth impregnant, it is characterized in that: by being coated with tackiness agent by adhesive applicator and forming through the glasscloth that adhesive applicator drying tunnel cures; Described tackiness agent is mixed by 1000 mass parts benzoxazine-maleinamide resin solutions, the linear metaphenylene unsaturated polyester of 15 ~ 30 mass parts, 0.2 ~ 2 mass parts promotor and 0.1 ~ 0.3 mass parts initiator and forms.Its preparation method comprises: prepare benzoxazine-maleinamide resin solution, preparation tackiness agent, by glasscloth by adhesive applicator adhesive coating, cure through the drying tunnel of adhesive applicator again, rolling, i.e. obtained pre-cured fiberglass cloth impregnant.Adopt the present invention, the storage at normal temperature time of benzoxazine resin base pre-cured fiberglass cloth impregnant, the fragility reducing post-treatment goods and demixing phenomenon can be improved; Impregnant is suitable for use as mold pressing, lamination and rolls electric insulation or structural composite material.
Description
Technical field
The invention belongs to the application of the composition based on polymer, relate to a kind of pre-cured fiberglass cloth impregnant and preparation method thereof.Pre-cured fiberglass cloth impregnant of the present invention is suitable for the industries such as electrical equipment and electrical, electron trade, oil, machinery and is used as mold pressing, lamination and rolls electric insulation or structural composite material.
Background technology
In the manufacturing processed of glasscloth matrix material (lamination, mold pressing and roll), generally all will through by resin solution painting process, obtained impreg is cut out and puts into heat pressing forming machines and be cured shaping.The glasscloth impregnant of industrial made benzoxazine-epoxy resin base, epoxy-phenolic aldehyde base, epoxy-imido grpup, because at room temperature the shelf-time is not long, have impact on them for the product performance after hot-forming, especially with the addition of the prepreg of dominant solidifying agent, usually used at 1 ~ 2 day or use at once, the longest only 3 ~ 5 days.In prior art, Chinese patent application CN102391201A discloses and adopts 4-hydroxy benzo cyclobutene to be raw material, has synthesized benzoxazine monomer and the resin thereof of the modification of 4-hydroxy benzo cyclobutene; Chinese patent application CN102432560A discloses and adopts laccol to be raw material, has synthesized resistance to elevated temperatures good laccol type benzoxazine monomer and resin thereof.The snappiness advantage that the benzoxazine monomer of these two kinds of structures and resin thereof are more comparatively given prominence to, can be used to change have and kind manufacture glasscloth matrix material (lamination, mold pressing and roll) product with it, although the manufacturing process comparative maturity all of these different resin system prepregs, but because cost is too high or be difficult to obtain because of starting material, be also not suitable for the manufacture of general engineered composite material in enormous quantities and insulating material product.It is short also to there is the prepreg shelf-time in prior art, needs low temperature cold to store, easily cause the composite products after solidification to have toughness is little, fragility is large shortcoming.
Summary of the invention
Object of the present invention is intended to overcome above-mentioned deficiency of the prior art, provides a kind of pre-cured fiberglass cloth impregnant and preparation method thereof.That is: the present invention has benzoxazine ring ring-opening polymerization in order to the prepreg played containing benzoxazine resin, reduce the outstanding process characteristic that small molecules thing (mainly water molecules) produces, for benzoxazine resin and unsaturated polyester resin (or other resins: epoxy, phenolic aldehyde etc.) mixed when producing the intermediates prepreg of post-treatment, the existing prepreg shelf-time is short, low temperature cold is needed to store, the composite products after solidification is easily caused to have toughness little, the shortcoming that fragility is large, propose with aminated compounds, MALEIC ANHYDRIDE, formaldehyde, phenolic compound is the substitute technology solution of Material synthesis benzoxazine-maleinamide resin (hereinafter referred to as " benzene-horse resin ") as pure benzoxazine resin, again using its composition mixed with unsaturated polyester resin as matrix resin, prepare glasscloth prepreg.
Content of the present invention is: a kind of pre-cured fiberglass cloth impregnant, is characterized in that: by being coated with tackiness agent by adhesive applicator and forming through the glasscloth that adhesive applicator drying tunnel cures;
Described tackiness agent is mixed by 1000 mass parts benzoxazine-maleinamide resin solutions, the linear metaphenylene unsaturated polyester of 15 ~ 30 mass parts, 0.2 ~ 2 mass parts promotor and 0.1 ~ 0.3 mass parts initiator and forms;
Described promotor is two or more the mixture in boron trifluoride ethylamine, glyoxal ethyline, 2-phenylimidazole, 2-ethyl-4-methylimidazole;
Described initiator be benzoyl peroxide, cyclohexanone peroxide any one;
Described benzoxazine-maleinamide resin solution is prepared by the following step:
A, batching: by aminated compounds: MALEIC ANHYDRIDE: formaldehyde: the mass ratio of phenolic compound=160 ~ 210:100:100 ~ 128:160 ~ 200 gets each component raw material, be mixed with the formalin that mass percent is 40% by formaldehyde; Get the solvent toluene of described formalin 2 times of quality, get the solvent acetone of described formalin 1.5 times of quality, for subsequent use;
B, synthesis: by aminated compounds, the solvent toluene of MALEIC ANHYDRIDE and 3/4 amount puts into reactor, under stirring (rapidly) be warming up to 70 ~ 95 DEG C reaction 1 ~ 2 hour, after being cooled to 5 ~ 25 DEG C again, add formalin again, control temperature is no more than 30 DEG C of reactions 0.5 ~ 2 hour, regulate pH=6 ~ 8, add the solvent toluene of phenolic compound and remaining 1/4 amount again, stirring reaction 2 ~ 5 hours at 80 ~ 100 DEG C of temperature, organic phase and aqueous phase is layered as after leaving standstill, the aqueous phase of removing reactor lower part, organic phase adds solvent acetone, stir 0.5 hour, i.e. obtained benzoxazine-maleinamide resin solution,
Described aminated compounds is aniline, quadrol, Ursol D, mphenylenediamine, 1,6 hexanediamines, 4,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenyl oxide, 4, two or more mixture in 4 '-diaminodiphenyl sulfide and DDS; Described aminated compounds may also be other monoamines existing, diamine, hydroxyl primary amine etc.;
Described phenolic compound is one or more the mixture in phenol, cresols, cardanol, laccol.
In content of the present invention: described tackiness agent is mixed by 1000 mass parts benzoxazine-maleinamide resin solutions, the linear metaphenylene unsaturated polyester of 15 ~ 30 mass parts, 0.2 ~ 2 mass parts promotor and 0.1 ~ 0.3 mass parts initiator and forms, and can replace with: described tackiness agent is mixed by 1200 mass parts benzoxazine-maleinamide resin solutions, the linear metaphenylene unsaturated polyester of 20 ~ 35 mass parts, 0.2 ~ 2 mass parts promotor, 0.1 ~ 0.3 mass parts initiator and 30 ~ 45 mass parts aniline basic ring phosphonitriles and forms;
The chemical structural formula of described aniline basic ring phosphonitrile is:
in formula: n=3 ~ 20.
In content of the present invention: described tackiness agent is by 1000 mass parts benzoxazine-maleinamide resin solutions, the linear metaphenylene unsaturated polyester of 15 ~ 30 mass parts, 0.2 ~ 2 mass parts promotor, and 0.1 ~ 0.3 mass parts initiator mixing composition, can also replace with: described tackiness agent is by 1500 mass parts benzoxazine-maleinamide resin solutions, the linear metaphenylene unsaturated polyester of 20 ~ 45 mass parts, 0.2 ~ 2 mass parts promotor, 0.1 ~ 0.3 mass parts initiator, 45 ~ 70 mass parts aniline basic ring phosphonitriles, and 100 ~ 150 mass parts epoxy resin mixing composition,
The chemical structural formula of described aniline basic ring phosphonitrile is:
in formula: n=3 ~ 20;
Described epoxy resin is one or both the mixture in bisphenol A epoxide resin, bisphenol f type epoxy resin.
In content of the present invention: described formaldehyde can replace with paraformaldehyde.
Another content of the present invention is: a kind of preparation method of pre-cured fiberglass cloth impregnant, it is characterized in that step is:
A, prepare benzoxazine-maleinamide resin solution:
Batching: by aminated compounds: MALEIC ANHYDRIDE: formaldehyde: the mass ratio of phenolic compound=160 ~ 210:100:100 ~ 128:160 ~ 200 gets each component raw material, formaldehyde is mixed with the formalin that mass percent is 40%; Get the solvent toluene of described formalin 2 times of quality, get the solvent acetone of described formalin 1.5 times of quality, for subsequent use;
Synthesis: by aminated compounds, the solvent toluene of MALEIC ANHYDRIDE and 3/4 amount puts into reactor, under stirring (rapidly) be warming up to 70 ~ 95 DEG C reaction 1 ~ 2 hour, after being cooled to 5 ~ 25 DEG C again, add formalin again, control temperature is no more than 30 DEG C of reactions 0.5 ~ 2 hour, regulate pH=6 ~ 8, add the solvent toluene of phenolic compound and remaining 1/4 amount again, stirring reaction 2 ~ 5 hours at 80 ~ 100 DEG C of temperature, organic phase and aqueous phase is layered as after leaving standstill, the aqueous phase of removing reactor lower part, organic phase adds solvent acetone, stir 0.5 hour, i.e. obtained benzoxazine-maleinamide resin solution,
Described aminated compounds is aniline, quadrol, Ursol D, mphenylenediamine, 1,6 hexanediamines, 4,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenyl oxide, 4, two or more mixture in 4 '-diaminodiphenyl sulfide and DDS; Described aminated compounds may also be other monoamines existing, diamine, hydroxyl primary amine etc.;
Described phenolic compound is one or more the mixture in phenol, cresols, cardanol, laccol;
B, preparation tackiness agent:
By 1000 mass parts benzoxazine-maleinamide resin solutions, the linear metaphenylene unsaturated polyester of 15 ~ 30 mass parts, 0.2 ~ 2 mass parts promotor and 0.1 ~ 0.3 mass parts initiator mixing and stirring i.e. obtained tackiness agent;
Described promotor is two or more the mixture in boron trifluoride ethylamine, glyoxal ethyline, 2-phenylimidazole, 2-ethyl-4-methylimidazole;
Described initiator be benzoyl peroxide, cyclohexanone peroxide any one;
C, prepare pre-cured fiberglass cloth impregnant:
Glasscloth is applied described tackiness agent by adhesive applicator, the drying tunnel length of described adhesive applicator is 36m, is divided into 3 sections, every section 12m, the stoving temperature scope of 3 sections is followed successively by 70 DEG C ~ 90 DEG C, 100 DEG C ~ 120 DEG C, 90 DEG C ~ 110 DEG C, the linear velocity speed of a motor vehicle of adhesive applicator is 3 ~ 12m/min, the glasscloth being coated with tackiness agent is cured through the drying tunnel of described adhesive applicator, rolling, i.e. obtained pre-cured fiberglass cloth impregnant.
In another content of the present invention: described tackiness agent is mixed by 1000 mass parts benzoxazine-maleinamide resin solutions, the linear metaphenylene unsaturated polyester of 15 ~ 30 mass parts, 0.2 ~ 2 mass parts promotor and 0.1 ~ 0.3 mass parts initiator and forms, and can replace with: described tackiness agent is mixed by 1200 mass parts benzoxazine-maleinamide resin solutions, the linear metaphenylene unsaturated polyester of 20 ~ 35 mass parts, 0.2 ~ 2 mass parts promotor, 0.1 ~ 0.3 mass parts initiator and 30 ~ 45 mass parts aniline basic ring phosphonitriles and forms;
The chemical structural formula of described aniline basic ring phosphonitrile is:
in formula: n=3 ~ 20.
In another content of the present invention: described tackiness agent is by 1000 mass parts benzoxazine-maleinamide resin solutions, the linear metaphenylene unsaturated polyester of 15 ~ 30 mass parts, 0.2 ~ 2 mass parts promotor, and 0.1 ~ 0.3 mass parts initiator mixing composition, can also replace with: described tackiness agent is by 1500 mass parts benzoxazine-maleinamide resin solutions, the linear metaphenylene unsaturated polyester of 20 ~ 45 mass parts, 0.2 ~ 2 mass parts promotor, 0.1 ~ 0.3 mass parts initiator, 45 ~ 70 mass parts aniline basic ring phosphonitriles, and 100 ~ 150 mass parts epoxy resin mixing composition,
Described aniline basic ring phosphonitrile is:
in formula: n=3 ~ 20;
Described epoxy resin is one or both the mixture in bisphenol A epoxide resin, bisphenol f type epoxy resin.
In another content of the present invention: described formaldehyde can replace with paraformaldehyde.
The part or all of of the prepolymer of following several basic structure is comprised in the benzoxazine-maleinamide resin solution of described preparation:
In above-mentioned each structural formula: m is 1 ~ 4; N is 1 ~ 5;
R
1, R
2, R
3and R
4for H or methyl, can be H or methyl, can be also H during difference, or be asynchronously methyl simultaneously;
Described glasscloth can be alkali-free plain weave glass cloth, alkali-free twill glasscloth.
The fabric width of described obtained pre-cured fiberglass cloth impregnant can be generally 1000mm ~ 1270mm.
The Resin Flow of described obtained pre-cured fiberglass cloth impregnant is 10 ~ 50mm, soluble resin content is 50% ~ 70%, volatile matter is≤5%.
Described obtained pre-cured fiberglass cloth impregnant can be used for the mold pressing of the industries such as electrical equipment and electrical, electron trade, oil, machinery, lamination and rolls the manufacture of electric insulation or structural composite material.
Compared with prior art, the present invention has features and beneficial effect:
(1) the present invention's linear metaphenylene unsaturated polyester of adopting benzene-horse resin and selectivity to add, promotor, the composition of initiator, add the composition that aniline basic ring phosphonitrile or " aniline basic ring phosphonitrile+epoxy resin " are formed further again, the glasscloth of coating can be made to carry out Procuring, the method is different from various resin system of the prior art and just carries out pure in desolventizing in glasscloth painting process, obtained pre-cured fiberglass cloth impregnant can (1 ~ 2 month) storage in room temperature for a long time, and it is not substantially inter-adhesive between glasscloth, also the coated of electrical equipment large-scale component can be carried out for large-size machine electrical company as work in-process more easily, be wound around, as large-scale dry type transformer turn-to-turn insulation, the manufacture of the special-shaped component of other vacuum impregnation pressure formings etc., functional, storage at normal temperature time of effective raising benzoxazine resin base pre-cured fiberglass cloth impregnant and reduce the defect such as fragility of post-treatment goods,
(2) the present invention adopts cheap conventional phenol, cresols, cardanol, MALEIC ANHYDRIDE, aniline, quadrol, Ursol D, diamines etc. are raw material, obtains the benzoxazine resin solution of the band maleinamide structure of certain flexibility; Next is, different according to purposes, laccol, 4,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenyl oxide, 4,4 '-diaminodiphenyl sulfide, DDS etc. or can greatly reduce use, thus making the manufacture pre-cured fiberglass cloth impregnant cost greatly reducing the formation of employing high price material become possibility, commercial effect is good;
(3) lamination that adopts pre-cured fiberglass cloth impregnant of the present invention to produce (mold pressing, roll) product has not easily layering between glasscloth, have certain flexibility and fragility is relatively low
(4) product preparation process of the present invention is simple, operation is easy, easy operation, pre-cured fiberglass cloth impregnant can be used for the mold pressing of the industries such as electrical equipment and electrical, electron trade, oil, machinery, lamination and rolls the manufacture of electric insulation or structural composite material, practical.
Embodiment
Embodiment given below is intended so that the invention will be further described; but can not be interpreted as it is limiting the scope of the invention; some nonessential improvement and adjustment that person skilled in art makes the present invention according to the content of the invention described above, still belong to protection scope of the present invention.
First part: synthesis benzene-horse resin solution (embodiment 1 ~ 15)
Embodiment 1:
By 160 ㎏ aminated compounds (aniline: mphenylenediamine: 1, 6 hexanediamines=4:3:1), 100 ㎏ MALEIC ANHYDRIDE drop into reactor together with 375 ㎏ toluene, under agitation, rapid temperature increases to 80 DEG C reaction 1 hour, after being cooled to 5 DEG C ~ 9 DEG C, add 250 ㎏ formalins (40%) again, control temperature is no more than 30 DEG C of reactions 0.5 ~ 1 hour, regulate pH=6 ~ 8, add 165 ㎏ phenolic compounds (phenol: cardanol=4:1) and 125 ㎏ toluene again, temperature 85 DEG C of stirring reactions 2 hours, organic phase and aqueous phase is layered as after leaving standstill, the water of removing reactor lower part, add 375 ㎏ acetone, stir 0.5 hour, obtain benzene-horse resin solution.
Embodiment 2:
By 160 ㎏ aminated compoundss (aniline: mphenylenediamine=4:3), 100 ㎏ MALEIC ANHYDRIDE drop into reactor together with 375 ㎏ toluene, under agitation, rapid temperature increases to 80 DEG C reaction 1 hour, after being cooled to 22 DEG C ~ 25 DEG C, add 250 ㎏ formalins (40%) again, control temperature is no more than 30 DEG C of reactions 0.5 ~ 1 hour, regulate pH=6 ~ 8, add 160 ㎏ phenolic compounds (phenol: cresols=1:2) and 125 ㎏ toluene again, temperature 85 DEG C of stirring reactions 2 hours, organic phase and aqueous phase is layered as after leaving standstill, the water of removing reactor lower part, add 375 ㎏ acetone, stir 0.5 hour, obtain benzene-horse resin solution.
Embodiment 3:
By 190 ㎏ aminated compounds (aniline: 1, 6 hexanediamines=2:3), 100 ㎏ MALEIC ANHYDRIDE drop into reactor together with 420 ㎏ toluene, under agitation, rapid temperature increases to 70 DEG C reaction 1.5 hours, after being cooled to 15 DEG C ~ 18 DEG C, add 280 ㎏ formalins (40%) again, control temperature is no more than 30 DEG C of reactions 1 hour, regulate pH=6 ~ 8, add 190 ㎏ phenolic compounds (phenol: cardanol=5:1) and 140 ㎏ toluene again, temperature 95 DEG C of stirring reactions 5 hours, organic phase and aqueous phase is layered as after leaving standstill, the water of removing reactor lower part, add 420 ㎏ acetone, stir 0.5 hour, obtain benzene-horse resin solution.
Embodiment 4:
By 210 ㎏ aminated compoundss (aniline: quadrol: Ursol D=3:1:1), 100 ㎏ MALEIC ANHYDRIDE drop into reactor together with 450 ㎏ toluene, under agitation, rapid temperature increases to 70 DEG C reaction 1 hour, after being cooled to 7 DEG C ~ 10 DEG C, add 300 ㎏ formalins (40%) again, control temperature is no more than 30 DEG C of reactions 1 hour, regulate pH=6 ~ 8, add 200 ㎏ phenolic compounds (phenol: cresols: laccol=6:3:1) and 150 ㎏ toluene again, temperature 80 DEG C of stirring reactions 2 hours, organic phase and aqueous phase is layered as after leaving standstill, the water of removing reactor lower part, add 450 ㎏ acetone, stir 0.5 hour, obtain benzene-horse resin solution.
Embodiment 5:
By 160 ㎏ aminated compoundss (aniline: quadrol=4:3), 100 ㎏ MALEIC ANHYDRIDE drop into reactor together with 375 ㎏ toluene, under agitation, rapid temperature increases to 80 DEG C reaction 1.5 hours, after being cooled to 18 DEG C ~ 20 DEG C, add 250 ㎏ formalins (40%) again, control temperature is no more than 30 DEG C of reactions 0.5 hour, regulate pH=6 ~ 8, add 165 ㎏ phenolic compounds (phenol: cresols=3:1) and 125 ㎏ toluene again, temperature 95 DEG C of stirring reactions 4 hours, organic phase and aqueous phase is layered as after leaving standstill, the water of removing reactor lower part, add 375 ㎏ acetone, stir 0.5 hour, obtain benzene-horse resin solution.
Embodiment 6:
By 160 ㎏ aminated compounds (aniline: quadrol: 1, 6 hexanediamines=8:2:1), 100 ㎏ MALEIC ANHYDRIDE drop into reactor together with 375 ㎏ toluene, under agitation, rapid temperature increases to 75 DEG C reaction 1.5 hours, after being cooled to 7 DEG C ~ 10 DEG C, add 250 ㎏ formalins (40%) again, control temperature is no more than 30 DEG C of reactions 0.5 hour, regulate pH=6 ~ 8, add 165 ㎏ phenol and 125 ㎏ toluene again, temperature 80 DEG C of stirring reactions 3 hours, organic phase and aqueous phase is layered as after leaving standstill, the water of removing reactor lower part, add 375 ㎏ acetone, stir 0.5 hour, obtain benzene-horse resin solution.
Embodiment 7:
By 160 ㎏ aminated compounds (aniline: quadrol: 4, 4 '-diaminodiphenyl oxide=3:1:1), 100 ㎏ MALEIC ANHYDRIDE drop into reactor together with 375 ㎏ toluene, under agitation, rapid temperature increases to 80 DEG C reaction 1.5 hours, after being cooled to 16 DEG C ~ 19 DEG C, add 250 ㎏ formalins (40%) again, control temperature is no more than 30 DEG C of reactions 0.5 hour, regulate pH=6 ~ 8, add 190 ㎏ phenolic compounds (phenol: cresols: cardanol: laccol=8:5:2:1) and 125 ㎏ toluene again, temperature 95 DEG C of stirring reactions 4 hours, organic phase and aqueous phase is layered as after leaving standstill, the water of removing reactor lower part, add 375 ㎏ acetone, stir 0.5 hour, obtain benzene-horse resin solution.
Embodiment 8:
By 180 ㎏ aminated compounds (aniline: 1, 6 hexanediamines: 4, 4 '-diaminodiphenyl sulfide=3:2:1), 100 ㎏ MALEIC ANHYDRIDE drop into reactor together with 412 ㎏ toluene, under agitation, rapid temperature increases to 95 DEG C reaction 1 hour, after being cooled to 9 DEG C ~ 11 DEG C, add 275 ㎏ formalins (40%) again, control temperature is no more than 30 DEG C of reactions 0.5 hour, regulate pH=6 ~ 8, add 180 ㎏ phenolic compounds (phenol: cresols=3:2) and 138 ㎏ toluene again, temperature 100 DEG C of stirring reactions 4 hours, organic phase and aqueous phase is layered as after leaving standstill, the water of removing reactor lower part, add 412 ㎏ acetone, stir 0.5 hour, obtain benzene-horse resin solution.
Embodiment 9:
By 210 ㎏ aminated compounds (aniline: mphenylenediamine: 1, 6 hexanediamines=3:1:1), 100 ㎏ MALEIC ANHYDRIDE drop into reactor together with 480 ㎏ toluene, under agitation, rapid temperature increases to 75 DEG C reaction 1.5 hours, after being cooled to 14 DEG C ~ 17 DEG C, add 320 ㎏ formalins (40%) again, control temperature is no more than 30 DEG C of reactions 1 hour, regulate pH=6 ~ 8, add 200 ㎏ phenolic compounds (phenol: cresols: laccol=5:2:1) and 160 ㎏ toluene again, temperature 80 DEG C of stirring reactions 5 hours, organic phase and aqueous phase is layered as after leaving standstill, the water of removing reactor lower part, add 480 ㎏ acetone, stir 0.5 hour, obtain benzene-horse resin solution.
Embodiment 10:
By 160 ㎏ aminated compounds (aniline: quadrol: 4, 4 '-diaminodiphenylmethane=6:3:1), 100 ㎏ MALEIC ANHYDRIDE drop into reactor together with 375 ㎏ toluene, under agitation, rapid temperature increases to 90 DEG C reaction 2 hours, after being cooled to 16 DEG C ~ 19 DEG C, add 250 ㎏ formalins (40%) again, control temperature is no more than 30 DEG C of reactions 1 hour, regulate pH=6 ~ 8, add 165 ㎏ phenolic compounds (cresols: cardanol=5:2) and 125 ㎏ toluene again, temperature 100 DEG C of stirring reactions 5 hours, organic phase and aqueous phase is layered as after leaving standstill, the water of removing reactor lower part, add 375 ㎏ acetone, stir 0.5 hour, obtain benzene-horse resin solution.
Embodiment 11:
By 160 ㎏ aminated compounds (aniline: Ursol D: 4, 4 '-diaminodiphenylsulfone(DDS)=5:5:1), 100 ㎏ MALEIC ANHYDRIDE drop into reactor together with 375 ㎏ toluene, under agitation, rapid temperature increases to 75 DEG C reaction 1.5 hours, after being cooled to 21 DEG C ~ 23 DEG C, add 250 ㎏ formalins (40%) again, control temperature is no more than 30 DEG C of reactions 0.5 hour, regulate pH=6 ~ 8, add 165 ㎏ phenolic compounds (phenol: laccol=5:1) and 125 ㎏ toluene again, temperature 80 DEG C of stirring reactions 3 hours, organic phase and aqueous phase is layered as after leaving standstill, the water of removing reactor lower part, add 375 ㎏ acetone, stir 0.5 hour, obtain benzene-horse resin solution.
Embodiment 12:
By 180 ㎏ aminated compounds (aniline: Ursol D: 4, 4 '-diaminodiphenylsulfone(DDS)=6:3:1), 100 ㎏ MALEIC ANHYDRIDE drop into reactor together with 412 ㎏ toluene, under agitation, rapid temperature increases to 90 DEG C reaction 1 hour, after being cooled to 6 DEG C ~ 9 DEG C, add 275 ㎏ formalins (40%) again, control temperature is no more than 30 DEG C of reactions 0.5 hour, regulate pH=6 ~ 8, add 180 ㎏ phenolic compounds (phenol: cresols: laccol=3:1:1) and 138 ㎏ toluene again, temperature 100 DEG C of stirring reactions 4 hours, organic phase and aqueous phase is layered as after leaving standstill, the water of removing reactor lower part, add 412 ㎏ acetone, stir 0.5 hour, obtain benzene-horse resin solution.
Embodiment 13:
By 195 ㎏ aminated compounds (aniline: quadrol: 4, 4 '-diaminodiphenyl oxide=5:3:1), 100 ㎏ MALEIC ANHYDRIDE drop into reactor together with 420 ㎏ toluene, under agitation, rapid temperature increases to 85 DEG C reaction 2 hours, after being cooled to 14 DEG C ~ 17 DEG C, add 280 ㎏ formalins (40%) again, control temperature is no more than 30 DEG C of reactions 1 hour, regulate pH=6 ~ 8, add 185 ㎏ phenolic compounds (phenol: cresols=4:1) and 140 ㎏ toluene again, temperature 95 DEG C of stirring reactions 4 hours, organic phase and aqueous phase is layered as after leaving standstill, the water of removing reactor lower part, add 420 ㎏ acetone, stir 0.5 hour, obtain benzene-horse resin solution.
Embodiment 14:
By 195 ㎏ aminated compounds (aniline: 1, 6 hexanediamines: 4, 4 '-diaminodiphenyl sulfide=2:1:1), 100 ㎏ MALEIC ANHYDRIDE drop into reactor together with 450 ㎏ toluene, under agitation, rapid temperature increases to 90 DEG C reaction 1.5 hours, after being cooled to 12 DEG C ~ 15 DEG C, add 300 ㎏ formalins (40%) again, control temperature is no more than 30 DEG C of reactions 1 hour, regulate pH=6 ~ 8, add 190 ㎏ cresols and 150 ㎏ toluene again, temperature 95 DEG C of stirring reactions 5 hours, organic phase and aqueous phase is layered as after leaving standstill, the water of removing reactor lower part, add 450 ㎏ acetone, stir 0.5 hour, obtain benzene-horse resin solution.
Embodiment 15:
By 180 ㎏ aminated compoundss (aniline: mphenylenediamine=3:2), 100 ㎏ MALEIC ANHYDRIDE drop into reactor together with 412 ㎏ toluene, under agitation, rapid temperature increases to 95 DEG C reaction 2 hours, after being cooled to 22 DEG C ~ 25 DEG C, add 275 ㎏ formalins (40%) again, control temperature is no more than 30 DEG C of reactions 1 hour, regulate pH=6 ~ 8, add 180 ㎏ phenolic compounds (phenol: cresols=1:2) and 138 ㎏ toluene again, temperature 90 DEG C of stirring reactions 3.5 hours, organic phase and aqueous phase is layered as after leaving standstill, the water of removing reactor lower part, add 412 ㎏ acetone, stir 0.5 hour, obtain benzene-horse resin solution.
Second section: the preparation of tackiness agent and the preparation (embodiment 16 ~ 30) of glasscloth prepreg
Embodiment 16 ~ 25:
1, the preparation of tackiness agent A: 1000 mass parts benzene-horse resin solution, the linear metaphenylene unsaturated polyester of 15 ~ 30 mass parts, 0.2 ~ 2 mass parts promotor, 0.1 ~ 0.3 mass parts initiator are stirred.
Described promotor be in boron trifluoride ethylamine, glyoxal ethyline, 2-phenylimidazole, 2-ethyl-4-methylimidazole any two or more mixture.
Described initiator be benzoyl peroxide, cyclohexanone peroxide any one.
2, pre-cured fiberglass cloth impregnant is prepared: by glasscloth by tackiness agent described in adhesive applicator applying step two, described adhesive applicator drying tunnel 36m, be divided into 3 sections, every section 12m, stoving temperature scope respectively is 70 DEG C ~ 90 DEG C, 100 DEG C ~ 120 DEG C, 90 DEG C ~ 110 DEG C, the linear velocity speed of a motor vehicle of adhesive applicator is 3 ~ 12m/min, be coated with the drying tunnel preliminary drying of glasscloth through adhesive applicator of tackiness agent, rolling, i.e. obtained pre-cured fiberglass cloth impregnant.The fabric width of pre-cured fiberglass cloth impregnant is 1000mm ~ 1270mm, Resin Flow is 10 ~ 50mm, soluble resin content is 50% ~ 70%, and volatile matter is≤5%.
Be below the tackiness agent A formula scale (unit is kg) of embodiment 16 ~ 25:
Embodiment 26 ~ 35:
1, the preparation of tackiness agent B: 1200 mass parts benzene-horse resin solution, the linear metaphenylene unsaturated polyester of 20 ~ 35 mass parts, 0.2 ~ 2 mass parts promotor, 0.1 ~ 0.3 mass parts initiator, 30 ~ 45 mass parts aniline basic ring phosphonitriles are stirred.
Described promotor be in boron trifluoride ethylamine, glyoxal ethyline, 2-phenylimidazole, 2-ethyl-4-methylimidazole any two or more mixture.
Described initiator be benzoyl peroxide, cyclohexanone peroxide any one.
2, pre-cured fiberglass cloth impregnant is prepared: by glasscloth by tackiness agent described in adhesive applicator applying step two, described adhesive applicator drying tunnel 36m, be divided into 3 sections, every section 12m, stoving temperature scope respectively is 70 DEG C ~ 90 DEG C, 100 DEG C ~ 120 DEG C, 90 DEG C ~ 110 DEG C, the linear velocity speed of a motor vehicle of adhesive applicator is 3 ~ 12m/min, be coated with the drying tunnel preliminary drying of glasscloth through adhesive applicator of tackiness agent, rolling, i.e. obtained pre-cured fiberglass cloth impregnant.The fabric width of described pre-cured fiberglass cloth impregnant is 1000mm ~ 1270mm, Resin Flow is 10 ~ 50mm, soluble resin content is 50% ~ 70%, and volatile matter is≤5%.
Be below the tackiness agent B formula scale (unit is kg) of embodiment 26 ~ 35:
Embodiment 36 ~ 45:
1, the preparation of tackiness agent C: 1500 mass parts benzene-horse resin solution, the linear metaphenylene unsaturated polyester of 20 ~ 45 mass parts, 0.2 ~ 2 mass parts promotor, 0.1 ~ 0.3 mass parts initiator, 45 ~ 70 mass parts aniline basic ring phosphonitriles, 100 ~ 150 mass parts epoxy resin are stirred.Epoxy resin is a kind of in bisphenol A epoxide resin, bisphenol f type epoxy resin or mixture.Promotor be in boron trifluoride ethylamine, glyoxal ethyline, 2-phenylimidazole, 2-ethyl-4-methylimidazole any two or more mixture.Initiator be benzoyl peroxide, cyclohexanone peroxide any one.
2, pre-cured fiberglass cloth impregnant is prepared: by glasscloth by tackiness agent described in adhesive applicator applying step two, described adhesive applicator drying tunnel 36m, be divided into 3 sections, every section 12m, stoving temperature scope respectively is 70 DEG C ~ 90 DEG C, 100 DEG C ~ 120 DEG C, 90 DEG C ~ 110 DEG C, the linear velocity speed of a motor vehicle of adhesive applicator is 3 ~ 12m/min, be coated with the drying tunnel preliminary drying of glasscloth through adhesive applicator of tackiness agent, rolling, i.e. obtained pre-cured fiberglass cloth impregnant.The fabric width of described pre-cured fiberglass cloth impregnant is 1000mm ~ 1270mm, Resin Flow is 10 ~ 50mm, soluble resin content is 50% ~ 70%, and volatile matter is≤5%.
Be below the tackiness agent C formula scale (unit is kg) of embodiment 36 ~ 45:
Carried out storing and post-treatment by prepreg prepared by above-described embodiment 16 ~ 45, measured result is through as follows:
Prepreg storage period and the fragility, the delamination table that are prepared into veneer sheet of embodiment 16 ~ 35
Note:
1, the tackiness agent major ingredient contrasting 1* is: pure benzoxazine (raw material 4,4 '-diaminodiphenylmethane, phenol, formaldehyde) resin.
2, the tackiness agent major ingredient contrasting 2** is: 90% benzoxazine (raw material 4,4 '-diaminodiphenylmethane, phenol, formaldehyde) resin and 10% unsaturated polyester resin.
3, the tackiness agent major ingredient contrasting 3*** is: 70% benzoxazine (raw material 4,4 '-diaminodiphenylmethane, phenol, formaldehyde) resin and 15% unsaturated polyester resin, 5% epoxy resin.
Embodiment 46:
A kind of pre-cured fiberglass cloth impregnant, by being coated with tackiness agent by adhesive applicator and forming through the glasscloth that adhesive applicator drying tunnel cures;
Described tackiness agent is mixed by 1000 mass parts benzoxazine-maleinamide resin solutions, the linear metaphenylene unsaturated polyester of 23 mass parts, 1.1 mass parts promotor and 0.2 mass parts initiator and forms;
Described benzoxazine-maleinamide resin solution is prepared by the following step:
A, batching: by aminated compounds: MALEIC ANHYDRIDE: formaldehyde: the mass ratio of phenolic compound=185:100:114:180 gets each component raw material, be mixed with the formalin that mass percent is 40% by formaldehyde; Get the solvent toluene of described formalin 2 times of quality, get the solvent acetone of described formalin 1.5 times of quality, for subsequent use;
B, synthesis: by aminated compounds, the solvent toluene of MALEIC ANHYDRIDE and 3/4 amount puts into reactor, under stirring (rapidly) be warming up to 85 DEG C reaction 1.5 hours, after being cooled to 15 DEG C again, add formalin again, control temperature is no more than 30 DEG C of reactions 1.2 hours, regulate pH=6 ~ 8, add the solvent toluene of phenolic compound and remaining 1/4 amount again, stirring reaction 4 hours at 90 DEG C of temperature, organic phase and aqueous phase is layered as after leaving standstill, the aqueous phase of removing reactor lower part, organic phase adds solvent acetone, stir 0.5 hour, i.e. obtained benzoxazine-maleinamide resin solution.
Embodiment 47:
A kind of pre-cured fiberglass cloth impregnant, by being coated with tackiness agent by adhesive applicator and forming through the glasscloth that adhesive applicator drying tunnel cures;
Described tackiness agent is mixed by 1000 mass parts benzoxazine-maleinamide resin solutions, the linear metaphenylene unsaturated polyester of 15 mass parts, 0.2 mass parts promotor and 0.1 mass parts initiator and forms;
Described benzoxazine-maleinamide resin solution is prepared by the following step:
A, batching: by aminated compounds: MALEIC ANHYDRIDE: formaldehyde: the mass ratio of phenolic compound=160:100:100:160 gets each component raw material, be mixed with the formalin that mass percent is 40% by formaldehyde; Get the solvent toluene of described formalin 2 times of quality, get the solvent acetone of described formalin 1.5 times of quality, for subsequent use;
B, synthesis: by aminated compounds, the solvent toluene of MALEIC ANHYDRIDE and 3/4 amount puts into reactor, under stirring (rapidly) be warming up to 70 DEG C reaction 2 hours, after being cooled to 5 DEG C again, add formalin again, control temperature is no more than 30 DEG C of reactions 2 hours, regulate pH=6 ~ 8, add the solvent toluene of phenolic compound and remaining 1/4 amount again, stirring reaction 5 hours at 80 DEG C of temperature, organic phase and aqueous phase is layered as after leaving standstill, the aqueous phase of removing reactor lower part, organic phase adds solvent acetone, stir 0.5 hour, i.e. obtained benzoxazine-maleinamide resin solution.
Embodiment 48:
A kind of pre-cured fiberglass cloth impregnant, by being coated with tackiness agent by adhesive applicator and forming through the glasscloth that adhesive applicator drying tunnel cures;
Described tackiness agent is mixed by 1000 mass parts benzoxazine-maleinamide resin solutions, the linear metaphenylene unsaturated polyester of 30 mass parts, 2 mass parts promotor and 0.3 mass parts initiator and forms;
Described benzoxazine-maleinamide resin solution is prepared by the following step:
A, batching: by aminated compounds: MALEIC ANHYDRIDE: formaldehyde: the mass ratio of phenolic compound=210:100:128:200 gets each component raw material, be mixed with the formalin that mass percent is 40% by formaldehyde; Get the solvent toluene of described formalin 2 times of quality, get the solvent acetone of described formalin 1.5 times of quality, for subsequent use;
B, synthesis: by aminated compounds, the solvent toluene of MALEIC ANHYDRIDE and 3/4 amount puts into reactor, under stirring (rapidly) be warming up to 95 DEG C reaction 1 hour, after being cooled to 25 DEG C again, add formalin again, control temperature is no more than 30 DEG C of reactions 0.5 hour, regulate pH=6 ~ 8, add the solvent toluene of phenolic compound and remaining 1/4 amount again, stirring reaction 2 hours at 100 DEG C of temperature, organic phase and aqueous phase is layered as after leaving standstill, the aqueous phase of removing reactor lower part, organic phase adds solvent acetone, stir 0.5 hour, i.e. obtained benzoxazine-maleinamide resin solution.
Embodiment 49 ~ 55:
A kind of pre-cured fiberglass cloth impregnant, by being coated with tackiness agent by adhesive applicator and forming through the glasscloth that adhesive applicator drying tunnel cures;
Described tackiness agent is mixed by 1000 mass parts benzoxazine-maleinamide resin solutions, the linear metaphenylene unsaturated polyester of 15 ~ 30 mass parts, 0.2 ~ 2 mass parts promotor and 0.1 ~ 0.3 mass parts initiator and forms;
The consumption of each component in embodiment 49 ~ 55 (unit of mass parts: gram) see the following form:
Described benzoxazine-maleinamide resin solution is prepared by the following step:
A, batching: by aminated compounds: MALEIC ANHYDRIDE: formaldehyde: the mass ratio of phenolic compound=160 ~ 210:100:100 ~ 128:160 ~ 200 gets each component raw material, be mixed with the formalin that mass percent is 40% by formaldehyde; Get the solvent toluene of described formalin 2 times of quality, get the solvent acetone of described formalin 1.5 times of quality, for subsequent use;
The consumption mass ratio of embodiment 49 ~ 55 benzoxazine used-maleinamide resin solution synthetic raw material sees the following form:
B, synthesis: by aminated compounds, the solvent toluene of MALEIC ANHYDRIDE and 3/4 amount puts into reactor, under stirring (rapidly) be warming up to 70 ~ 95 DEG C reaction 1 ~ 2 hour, after being cooled to 5 ~ 25 DEG C again, add formalin again, control temperature is no more than 30 DEG C of reactions 0.5 ~ 2 hour, regulate pH=6 ~ 8, add the solvent toluene of phenolic compound and remaining 1/4 amount again, stirring reaction 2 ~ 5 hours at 80 ~ 100 DEG C of temperature, organic phase and aqueous phase is layered as after leaving standstill, the aqueous phase of removing reactor lower part, organic phase adds solvent acetone, stir 0.5 hour, i.e. obtained benzoxazine-maleinamide resin solution.
In above-described embodiment 46 ~ 55: described promotor is two or more the mixture in boron trifluoride ethylamine, glyoxal ethyline, 2-phenylimidazole, 2-ethyl-4-methylimidazole;
In above-described embodiment 46 ~ 55: described initiator be benzoyl peroxide, cyclohexanone peroxide any one;
In above-described embodiment 46 ~ 55: described aminated compounds is aniline, quadrol, Ursol D, mphenylenediamine, 1,6 hexanediamines, 4,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenyl oxide, 4, two or more mixture in 4 '-diaminodiphenyl sulfide and DDS; Described aminated compounds may also be other monoamines existing, diamine, hydroxyl primary amine etc.;
In above-described embodiment 46 ~ 55: described phenolic compound is one or more the mixture in phenol, cresols, cardanol, laccol.
Embodiment 56:
A kind of pre-cured fiberglass cloth impregnant, by being coated with tackiness agent by adhesive applicator and forming through the glasscloth that adhesive applicator drying tunnel cures; Described tackiness agent is mixed by 1200 mass parts benzoxazine-maleinamide resin solutions, the linear metaphenylene unsaturated polyester of 28 mass parts, 1.6 mass parts promotor, 0.2 mass parts initiator and 37 mass parts aniline basic ring phosphonitriles and forms; Other omits with arbitrary in 46 ~ 55.
The chemical structural formula of described aniline basic ring phosphonitrile is:
in formula: n=3 ~ 20;
Embodiment 57:
A kind of pre-cured fiberglass cloth impregnant, by being coated with tackiness agent by adhesive applicator and forming through the glasscloth that adhesive applicator drying tunnel cures; Described tackiness agent is mixed by 1200 mass parts benzoxazine-maleinamide resin solutions, the linear metaphenylene unsaturated polyester of 35 mass parts, 2 mass parts promotor, 0.3 mass parts initiator and 45 mass parts aniline basic ring phosphonitriles and forms; Other omits with arbitrary in 46 ~ 55.
Embodiment 58:
A kind of pre-cured fiberglass cloth impregnant, by being coated with tackiness agent by adhesive applicator and forming through the glasscloth that adhesive applicator drying tunnel cures; Described tackiness agent is mixed by 1200 mass parts benzoxazine-maleinamide resin solutions, the linear metaphenylene unsaturated polyester of 20 mass parts, 0.2 mass parts promotor, 0.1 mass parts initiator and 30 mass parts aniline basic ring phosphonitriles and forms; Other omits with arbitrary in 46 ~ 55.
Embodiment 59 ~ 65:
A kind of pre-cured fiberglass cloth impregnant, by being coated with tackiness agent by adhesive applicator and forming through the glasscloth that adhesive applicator drying tunnel cures; Described tackiness agent is mixed by 1200 mass parts benzoxazine-maleinamide resin solutions, the linear metaphenylene unsaturated polyester of 20 ~ 35 mass parts, 0.2 ~ 2 mass parts promotor, 0.1 ~ 0.3 mass parts initiator and 30 ~ 45 mass parts aniline basic ring phosphonitriles and forms;
Other omits with arbitrary in 46 ~ 55;
The consumption of each component in embodiment 59 ~ 65 (unit of mass parts: gram) see the following form:
Embodiment 66:
A kind of pre-cured fiberglass cloth impregnant, by being coated with tackiness agent by adhesive applicator and forming through the glasscloth that adhesive applicator drying tunnel cures; Described tackiness agent is mixed by 1500 mass parts benzoxazine-maleinamide resin solutions, the linear metaphenylene unsaturated polyester of 33 mass parts, 1.1 mass parts promotor, 0.2 mass parts initiator, 58 mass parts aniline basic ring phosphonitriles and 125 mass parts epoxy resin and forms;
The chemical structural formula of described aniline basic ring phosphonitrile is:
in formula: n=3 ~ 20;
Described epoxy resin is one or both the mixture in bisphenol A epoxide resin, bisphenol f type epoxy resin;
Other omits with arbitrary in 46 ~ 55.
Embodiment 67:
A kind of pre-cured fiberglass cloth impregnant, by being coated with tackiness agent by adhesive applicator and forming through the glasscloth that adhesive applicator drying tunnel cures; Described tackiness agent is mixed by 1500 mass parts benzoxazine-maleinamide resin solutions, the linear metaphenylene unsaturated polyester of 20 mass parts, 0.2 mass parts promotor, 0.1 mass parts initiator, 45 mass parts aniline basic ring phosphonitriles and 100 mass parts epoxy resin and forms;
Other omits with arbitrary or embodiment 66 in 46 ~ 55.
Embodiment 68:
A kind of pre-cured fiberglass cloth impregnant, by being coated with tackiness agent by adhesive applicator and forming through the glasscloth that adhesive applicator drying tunnel cures; Described tackiness agent is mixed by 1500 mass parts benzoxazine-maleinamide resin solutions, the linear metaphenylene unsaturated polyester of 45 mass parts, 2 mass parts promotor, 0.3 mass parts initiator, 70 mass parts aniline basic ring phosphonitriles and 150 mass parts epoxy resin and forms;
Other omits with arbitrary or embodiment 66 in 46 ~ 55.
Embodiment 69 ~ 75:
A kind of pre-cured fiberglass cloth impregnant, by being coated with tackiness agent by adhesive applicator and forming through the glasscloth that adhesive applicator drying tunnel cures; Described tackiness agent is mixed by 1500 mass parts benzoxazine-maleinamide resin solutions, the linear metaphenylene unsaturated polyester of 20 ~ 45 mass parts, 0.2 ~ 2 mass parts promotor, 0.1 ~ 0.3 mass parts initiator, 45 ~ 70 mass parts aniline basic ring phosphonitriles and 100 ~ 150 mass parts epoxy resin and forms;
The consumption of each component in embodiment 59 ~ 65 (unit of mass parts: gram) see the following form:
Other omits with arbitrary or embodiment 66 in 46 ~ 55.
Embodiment 76:
A preparation method for pre-cured fiberglass cloth impregnant, step is:
A, prepare benzoxazine-maleinamide resin solution:
Batching: by aminated compounds: MALEIC ANHYDRIDE: formaldehyde: the mass ratio of phenolic compound=185:100:114:180 gets each component raw material, formaldehyde is mixed with the formalin that mass percent is 40%; Get the solvent toluene of described formalin 2 times of quality, get the solvent acetone of described formalin 1.5 times of quality, for subsequent use;
Synthesis: by aminated compounds, the solvent toluene of MALEIC ANHYDRIDE and 3/4 amount puts into reactor, under stirring (rapidly) be warming up to 85 DEG C reaction 1.5 hours, after being cooled to 15 DEG C again, add formalin again, control temperature is no more than 30 DEG C of reactions 1.2 hours, regulate pH=6 ~ 8, add the solvent toluene of phenolic compound and remaining 1/4 amount again, stirring reaction 3.5 hours at 90 DEG C of temperature, organic phase and aqueous phase is layered as after leaving standstill, the aqueous phase of removing reactor lower part, organic phase adds solvent acetone, stir 0.5 hour, i.e. obtained benzoxazine-maleinamide resin solution,
B, preparation tackiness agent:
By 1000 mass parts benzoxazine-maleinamide resin solutions, the linear metaphenylene unsaturated polyester of 27 mass parts, 1.1 mass parts promotor and 0.2 mass parts initiator mixing and stirring i.e. obtained tackiness agent;
C, prepare pre-cured fiberglass cloth impregnant:
Glasscloth is applied described tackiness agent by adhesive applicator, the drying tunnel length of described adhesive applicator is 36m, is divided into 3 sections, every section 12m, the stoving temperature scope of 3 sections is followed successively by 70 DEG C ~ 90 DEG C, 100 DEG C ~ 120 DEG C, 90 DEG C ~ 110 DEG C, the linear velocity speed of a motor vehicle of adhesive applicator is 7.5m/min, the glasscloth being coated with tackiness agent is cured through the drying tunnel of described adhesive applicator, rolling, i.e. obtained pre-cured fiberglass cloth impregnant.
Embodiment 77:
A preparation method for pre-cured fiberglass cloth impregnant, step is:
A, prepare benzoxazine-maleinamide resin solution:
Batching: by aminated compounds: MALEIC ANHYDRIDE: formaldehyde: the mass ratio of phenolic compound=160:100:100:160 gets each component raw material, formaldehyde is mixed with the formalin that mass percent is 40%; Get the solvent toluene of described formalin 2 times of quality, get the solvent acetone of described formalin 1.5 times of quality, for subsequent use;
Synthesis: by aminated compounds, the solvent toluene of MALEIC ANHYDRIDE and 3/4 amount puts into reactor, under stirring (rapidly) be warming up to 70 DEG C reaction 2 hours, after being cooled to 5 DEG C again, add formalin again, control temperature is no more than 30 DEG C of reactions 2 hours, regulate pH=6 ~ 8, add the solvent toluene of phenolic compound and remaining 1/4 amount again, stirring reaction 5 hours at 80 DEG C of temperature, organic phase and aqueous phase is layered as after leaving standstill, the aqueous phase of removing reactor lower part, organic phase adds solvent acetone, stir 0.5 hour, i.e. obtained benzoxazine-maleinamide resin solution,
B, preparation tackiness agent:
By 1000 mass parts benzoxazine-maleinamide resin solutions, the linear metaphenylene unsaturated polyester of 15 mass parts, 0.2 mass parts promotor and 0.1 mass parts initiator mixing and stirring i.e. obtained tackiness agent;
C, prepare pre-cured fiberglass cloth impregnant:
Glasscloth is applied described tackiness agent by adhesive applicator, the drying tunnel length of described adhesive applicator is 36m, is divided into 3 sections, every section 12m, the stoving temperature scope of 3 sections is followed successively by 70 DEG C ~ 90 DEG C, 100 DEG C ~ 120 DEG C, 90 DEG C ~ 110 DEG C, the linear velocity speed of a motor vehicle of adhesive applicator is 3m/min, the glasscloth being coated with tackiness agent is cured through the drying tunnel of described adhesive applicator, rolling, i.e. obtained pre-cured fiberglass cloth impregnant.
Embodiment 78:
A preparation method for pre-cured fiberglass cloth impregnant, step is:
A, prepare benzoxazine-maleinamide resin solution:
Batching: by aminated compounds: MALEIC ANHYDRIDE: formaldehyde: the mass ratio of phenolic compound=210:100:128:200 gets each component raw material, formaldehyde is mixed with the formalin that mass percent is 40%; Get the solvent toluene of described formalin 2 times of quality, get the solvent acetone of described formalin 1.5 times of quality, for subsequent use;
Synthesis: by aminated compounds, the solvent toluene of MALEIC ANHYDRIDE and 3/4 amount puts into reactor, under stirring (rapidly) be warming up to 95 DEG C reaction 1 hour, after being cooled to 25 DEG C again, add formalin again, control temperature is no more than 30 DEG C of reactions 0.5 hour, regulate pH=6 ~ 8, add the solvent toluene of phenolic compound and remaining 1/4 amount again, stirring reaction 2 hours at 100 DEG C of temperature, organic phase and aqueous phase is layered as after leaving standstill, the aqueous phase of removing reactor lower part, organic phase adds solvent acetone, stir 0.5 hour, i.e. obtained benzoxazine-maleinamide resin solution,
B, preparation tackiness agent:
By 1000 mass parts benzoxazine-maleinamide resin solutions, the linear metaphenylene unsaturated polyester of 30 mass parts, 2 mass parts promotor and 0.3 mass parts initiator mixing and stirring i.e. obtained tackiness agent;
C, prepare pre-cured fiberglass cloth impregnant:
Glasscloth is applied described tackiness agent by adhesive applicator, the drying tunnel length of described adhesive applicator is 36m, is divided into 3 sections, every section 12m, the stoving temperature scope of 3 sections is followed successively by 70 DEG C ~ 90 DEG C, 100 DEG C ~ 120 DEG C, 90 DEG C ~ 110 DEG C, the linear velocity speed of a motor vehicle of adhesive applicator is 12m/min, the glasscloth being coated with tackiness agent is cured through the drying tunnel of described adhesive applicator, rolling, i.e. obtained pre-cured fiberglass cloth impregnant.
Embodiment 79 ~ 85:
A preparation method for pre-cured fiberglass cloth impregnant, step is:
A, prepare benzoxazine-maleinamide resin solution:
Batching: by aminated compounds: MALEIC ANHYDRIDE: formaldehyde: the mass ratio of phenolic compound=160 ~ 210:100:100 ~ 128:160 ~ 200 gets each component raw material, formaldehyde is mixed with the formalin that mass percent is 40%; Get the solvent toluene of described formalin 2 times of quality, get the solvent acetone of described formalin 1.5 times of quality, for subsequent use;
The consumption mass ratio of embodiment 79 ~ 85 benzoxazine used-maleinamide resin solution synthetic raw material sees the following form:
Synthesis: by aminated compounds, the solvent toluene of MALEIC ANHYDRIDE and 3/4 amount puts into reactor, under stirring (rapidly) be warming up to 70 ~ 95 DEG C reaction 1 ~ 2 hour, after being cooled to 5 ~ 25 DEG C again, add formalin again, control temperature is no more than 30 DEG C of reactions 0.5 ~ 2 hour, regulate pH=6 ~ 8, add the solvent toluene of phenolic compound and remaining 1/4 amount again, stirring reaction 2 ~ 5 hours at 80 ~ 100 DEG C of temperature, organic phase and aqueous phase is layered as after leaving standstill, the aqueous phase of removing reactor lower part, organic phase adds solvent acetone, stir 0.5 hour, i.e. obtained benzoxazine-maleinamide resin solution,
B, preparation tackiness agent:
By 1000 mass parts benzoxazine-maleinamide resin solutions, the linear metaphenylene unsaturated polyester of 15 ~ 30 mass parts, 0.2 ~ 2 mass parts promotor and 0.1 ~ 0.3 mass parts initiator mixing and stirring i.e. obtained tackiness agent;
The consumption of each component in embodiment 79 ~ 85 (unit of mass parts: gram) see the following form:
C, prepare pre-cured fiberglass cloth impregnant:
Glasscloth is applied described tackiness agent by adhesive applicator, the drying tunnel length of described adhesive applicator is 36m, is divided into 3 sections, every section 12m, the stoving temperature scope of 3 sections is followed successively by 70 DEG C ~ 90 DEG C, 100 DEG C ~ 120 DEG C, 90 DEG C ~ 110 DEG C, the linear velocity speed of a motor vehicle of adhesive applicator is 3 ~ 12m/min, the glasscloth being coated with tackiness agent is cured through the drying tunnel of described adhesive applicator, rolling, i.e. obtained pre-cured fiberglass cloth impregnant.
In above-described embodiment 76 ~ 85: described aminated compounds is aniline, quadrol, Ursol D, mphenylenediamine, 1,6 hexanediamines, 4,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenyl oxide, 4, two or more mixture in 4 '-diaminodiphenyl sulfide and DDS; Described aminated compounds may also be other monoamines existing, diamine, hydroxyl primary amine etc.;
In above-described embodiment 76 ~ 85: described phenolic compound is one or more the mixture in phenol, cresols, cardanol, laccol;
In above-described embodiment 76 ~ 85: described promotor is two or more the mixture in boron trifluoride ethylamine, glyoxal ethyline, 2-phenylimidazole, 2-ethyl-4-methylimidazole;
In above-described embodiment 76 ~ 85: described initiator be benzoyl peroxide, cyclohexanone peroxide any one;
Embodiment 86 ~ 95:
A preparation method for pre-cured fiberglass cloth impregnant, described tackiness agent is mixed by 1200 mass parts benzoxazine-maleinamide resin solutions, the linear metaphenylene unsaturated polyester of 20 ~ 35 mass parts, 0.2 ~ 2 mass parts promotor, 0.1 ~ 0.3 mass parts initiator and 30 ~ 45 mass parts aniline basic ring phosphonitriles and forms; The consumption of each component in embodiment 86 ~ 95 is respectively with embodiment 56 ~ 65; Other omits with arbitrary in 76 ~ 85.
Embodiment 96 ~ 105:
A preparation method for pre-cured fiberglass cloth impregnant, described tackiness agent is mixed by 1500 mass parts benzoxazine-maleinamide resin solutions, the linear metaphenylene unsaturated polyester of 20 ~ 45 mass parts, 0.2 ~ 2 mass parts promotor, 0.1 ~ 0.3 mass parts initiator, 45 ~ 70 mass parts aniline basic ring phosphonitriles and 100 ~ 150 mass parts epoxy resin and forms; The consumption of each component in embodiment 96 ~ 105 is respectively with embodiment 66 ~ 75;
Other omits with arbitrary in 76 ~ 85.
In above-described embodiment 46 ~ 105: described formaldehyde can replace with paraformaldehyde.
Described glasscloth can be alkali-free plain weave glass cloth, alkali-free twill glasscloth.
In above-described embodiment 46 ~ 105: the fabric width of described obtained pre-cured fiberglass cloth impregnant can be generally 1000mm ~ 1270mm.
In above-described embodiment 46 ~ 105: the Resin Flow of described obtained pre-cured fiberglass cloth impregnant is 10 ~ 50mm, soluble resin content is 50% ~ 70%, volatile matter is≤5%.
Described obtained pre-cured fiberglass cloth impregnant can be used for the mold pressing of the industries such as electrical equipment and electrical, electron trade, oil, machinery, lamination and rolls the manufacture of electric insulation or structural composite material.
In above-described embodiment: in the percentage adopted, do not indicate especially, be quality (weight) percentage; In the ratio adopted, do not indicate especially, be quality (weight) ratio; Described quality (weight) part can be all gram or kilogram.
In above-described embodiment: the processing parameter (temperature, time, concentration etc.) in each step and each amounts of components numerical value etc. are scope, and any point is all applicable.
The concrete same prior art of technology contents described in content of the present invention and above-described embodiment, described starting material are commercially available prod.
The invention is not restricted to above-described embodiment, all can implement described in content of the present invention and there is described good result.
Claims (8)
1. a pre-cured fiberglass cloth impregnant, is characterized in that: by being coated with tackiness agent by adhesive applicator and forming through the glasscloth that adhesive applicator drying tunnel cures;
Described tackiness agent is mixed by 1000 mass parts benzoxazine-maleinamide resin solutions, the linear metaphenylene unsaturated polyester of 15 ~ 30 mass parts, 0.2 ~ 2 mass parts promotor and 0.1 ~ 0.3 mass parts initiator and forms;
Described promotor is two or more the mixture in boron trifluoride ethylamine, glyoxal ethyline, 2-phenylimidazole, 2-ethyl-4-methylimidazole;
Described initiator be benzoyl peroxide, cyclohexanone peroxide any one;
Described benzoxazine-maleinamide resin solution is prepared by the following step:
A, batching: by aminated compounds: MALEIC ANHYDRIDE: formaldehyde: the mass ratio of phenolic compound=160 ~ 210:100:100 ~ 128:160 ~ 200 gets each component raw material, be mixed with the formalin that mass percent is 40% by formaldehyde; Get the solvent toluene of described formalin 2 times of quality, get the solvent acetone of described formalin 1.5 times of quality, for subsequent use;
B, synthesis: by aminated compounds, the solvent toluene of MALEIC ANHYDRIDE and 3/4 amount puts into reactor, 70 ~ 95 DEG C of reactions 1 ~ 2 hour is warming up under stirring, after being cooled to 5 ~ 25 DEG C again, add formalin again, control temperature is no more than 30 DEG C of reactions 0.5 ~ 2 hour, regulate pH=6 ~ 8, add the solvent toluene of phenolic compound and remaining 1/4 amount again, stirring reaction 2 ~ 5 hours at 80 ~ 100 DEG C of temperature, organic phase and aqueous phase is layered as after leaving standstill, the aqueous phase of removing reactor lower part, organic phase adds solvent acetone, stir 0.5 hour, i.e. obtained benzoxazine-maleinamide resin solution,
Described aminated compounds is aniline, quadrol, Ursol D, mphenylenediamine, 1,6 hexanediamines, 4,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenyl oxide, 4, two or more mixture in 4 '-diaminodiphenyl sulfide and DDS;
Described phenolic compound is one or more the mixture in phenol, cresols, cardanol, laccol.
2. by pre-cured fiberglass cloth impregnant described in claim 1, it is characterized in that: described tackiness agent is by 1000 mass parts benzoxazine-maleinamide resin solutions, the linear metaphenylene unsaturated polyester of 15 ~ 30 mass parts, 0.2 ~ 2 mass parts promotor, and 0.1 ~ 0.3 mass parts initiator mixing composition, replace with: described tackiness agent is by 1200 mass parts benzoxazine-maleinamide resin solutions, the linear metaphenylene unsaturated polyester of 20 ~ 35 mass parts, 0.2 ~ 2 mass parts promotor, 0.1 ~ 0.3 mass parts initiator, and 30 ~ 45 mass parts aniline basic ring phosphonitrile mixing composition,
The chemical structural formula of described aniline basic ring phosphonitrile is:
in formula: n=3 ~ 20.
3. by pre-cured fiberglass cloth impregnant described in claim 1, it is characterized in that: described tackiness agent is by 1000 mass parts benzoxazine-maleinamide resin solutions, the linear metaphenylene unsaturated polyester of 15 ~ 30 mass parts, 0.2 ~ 2 mass parts promotor, and 0.1 ~ 0.3 mass parts initiator mixing composition, replace with: described tackiness agent is by 1500 mass parts benzoxazine-maleinamide resin solutions, the linear metaphenylene unsaturated polyester of 20 ~ 45 mass parts, 0.2 ~ 2 mass parts promotor, 0.1 ~ 0.3 mass parts initiator, 45 ~ 70 mass parts aniline basic ring phosphonitriles, and 100 ~ 150 mass parts epoxy resin mixing composition,
The chemical structural formula of described aniline basic ring phosphonitrile is:
in formula: n=3 ~ 20;
Described epoxy resin is one or both the mixture in bisphenol A epoxide resin, bisphenol f type epoxy resin.
4., by pre-cured fiberglass cloth impregnant described in claim 1,2 or 3, it is characterized in that: described formaldehyde replaces with paraformaldehyde.
5. a preparation method for pre-cured fiberglass cloth impregnant, is characterized in that step is:
A, prepare benzoxazine-maleinamide resin solution:
Batching: by aminated compounds: MALEIC ANHYDRIDE: formaldehyde: the mass ratio of phenolic compound=160 ~ 210:100:100 ~ 128:160 ~ 200 gets each component raw material, formaldehyde is mixed with the formalin that mass percent is 40%; Get the solvent toluene of described formalin 2 times of quality, get the solvent acetone of described formalin 1.5 times of quality, for subsequent use;
Synthesis: by aminated compounds, the solvent toluene of MALEIC ANHYDRIDE and 3/4 amount puts into reactor, 70 ~ 95 DEG C of reactions 1 ~ 2 hour is warming up under stirring, after being cooled to 5 ~ 25 DEG C again, add formalin again, control temperature is no more than 30 DEG C of reactions 0.5 ~ 2 hour, regulate pH=6 ~ 8, add the solvent toluene of phenolic compound and remaining 1/4 amount again, stirring reaction 2 ~ 5 hours at 80 ~ 100 DEG C of temperature, organic phase and aqueous phase is layered as after leaving standstill, the aqueous phase of removing reactor lower part, organic phase adds solvent acetone, stir 0.5 hour, i.e. obtained benzoxazine-maleinamide resin solution,
Described aminated compounds is aniline, quadrol, Ursol D, mphenylenediamine, 1,6 hexanediamines, 4,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenyl oxide, 4, two or more mixture in 4 '-diaminodiphenyl sulfide and DDS;
Described phenolic compound is one or more the mixture in phenol, cresols, cardanol, laccol;
B, preparation tackiness agent:
By 1000 mass parts benzoxazine-maleinamide resin solutions, the linear metaphenylene unsaturated polyester of 15 ~ 30 mass parts, 0.2 ~ 2 mass parts promotor and 0.1 ~ 0.3 mass parts initiator mixing and stirring i.e. obtained tackiness agent;
Described promotor is two or more the mixture in boron trifluoride ethylamine, glyoxal ethyline, 2-phenylimidazole, 2-ethyl-4-methylimidazole;
Described initiator be benzoyl peroxide, cyclohexanone peroxide any one;
C, prepare pre-cured fiberglass cloth impregnant:
Glasscloth is applied described tackiness agent by adhesive applicator, the drying tunnel length of described adhesive applicator is 36m, is divided into 3 sections, every section 12m, the stoving temperature scope of 3 sections is followed successively by 70 DEG C ~ 90 DEG C, 100 DEG C ~ 120 DEG C, 90 DEG C ~ 110 DEG C, the linear velocity speed of a motor vehicle of adhesive applicator is 3 ~ 12m/min, the glasscloth being coated with tackiness agent is cured through the drying tunnel of described adhesive applicator, rolling, i.e. obtained pre-cured fiberglass cloth impregnant.
6. by the preparation method of pre-cured fiberglass cloth impregnant described in claim 5, it is characterized in that: by 1000 mass parts benzoxazine-maleinamide resin solutions, the linear metaphenylene unsaturated polyester of 15 ~ 30 mass parts, 0.2 ~ 2 mass parts promotor, and the i.e. obtained tackiness agent of 0.1 ~ 0.3 mass parts initiator mixing and stirring, replace with: by 1200 mass parts benzoxazine-maleinamide resin solutions, the linear metaphenylene unsaturated polyester of 20 ~ 35 mass parts, 0.2 ~ 2 mass parts promotor, 0.1 ~ 0.3 mass parts initiator, and the i.e. obtained tackiness agent of 30 ~ 45 mass parts aniline basic ring phosphonitrile mixing and stirring,
The chemical structural formula of described aniline basic ring phosphonitrile is:
in formula: n=3 ~ 20.
7. by the preparation method of pre-cured fiberglass cloth impregnant described in claim 5, it is characterized in that: by 1000 mass parts benzoxazine-maleinamide resin solutions, the linear metaphenylene unsaturated polyester of 15 ~ 30 mass parts, 0.2 ~ 2 mass parts promotor, and the i.e. obtained tackiness agent of 0.1 ~ 0.3 mass parts initiator mixing and stirring, replace with: by 1500 mass parts benzoxazine-maleinamide resin solutions, the linear metaphenylene unsaturated polyester of 20 ~ 45 mass parts, 0.2 ~ 2 mass parts promotor, 0.1 ~ 0.3 mass parts initiator, 45 ~ 70 mass parts aniline basic ring phosphonitriles, and the i.e. obtained tackiness agent of 100 ~ 150 mass parts epoxy resin mixing and stirring,
The chemical structural formula of described aniline basic ring phosphonitrile is:
in formula: n=3 ~ 20;
Described epoxy resin is one or both the mixture in bisphenol A epoxide resin, bisphenol f type epoxy resin.
8., by the preparation method of pre-cured fiberglass cloth impregnant described in claim 5,6 or 7, it is characterized in that: described formaldehyde replaces with paraformaldehyde.
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| CN113059892B (en) * | 2021-04-13 | 2022-04-29 | 浙江博菲电气股份有限公司 | Manufacturing method of plasticity-enhanced composite material for magnetic conductive forming part |
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| CN103232705A (en) * | 2013-04-22 | 2013-08-07 | 苏州生益科技有限公司 | High-frequency resin composition as well as semi-cured sheet and laminated board manufactured by high-frequency resin composition |
| CN103265791A (en) * | 2013-05-29 | 2013-08-28 | 苏州生益科技有限公司 | Thermosetting resin composition for integrated circuit as well as prepreg and laminated board both fabricated by using composition |
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| US20090274916A1 (en) * | 2006-07-20 | 2009-11-05 | Showa Highpolymer Co., Ltd | Phosphorus-containing benzoxazine compound, process for production thereof, curable resin composition, cured article, and laminate plate |
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| CN103223762A (en) * | 2013-04-01 | 2013-07-31 | 四川东材科技集团股份有限公司 | Preparation method of glass fiber cloth laminate with epoxide-group benzoxazine |
| CN103232705A (en) * | 2013-04-22 | 2013-08-07 | 苏州生益科技有限公司 | High-frequency resin composition as well as semi-cured sheet and laminated board manufactured by high-frequency resin composition |
| CN103265791A (en) * | 2013-05-29 | 2013-08-28 | 苏州生益科技有限公司 | Thermosetting resin composition for integrated circuit as well as prepreg and laminated board both fabricated by using composition |
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