CN103937162A - Low-temperature resin composition and preparation method thereof - Google Patents
Low-temperature resin composition and preparation method thereof Download PDFInfo
- Publication number
- CN103937162A CN103937162A CN201410145795.5A CN201410145795A CN103937162A CN 103937162 A CN103937162 A CN 103937162A CN 201410145795 A CN201410145795 A CN 201410145795A CN 103937162 A CN103937162 A CN 103937162A
- Authority
- CN
- China
- Prior art keywords
- mass parts
- low
- temperature
- resin
- resins
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a low-temperature resin composition and a preparation method thereof. The preparation method of the low-temperature resin composition comprises the steps of adding 15 parts by weight of low-molecular weight polyester resin, 30-50 parts by weight of phenolic novolac resin, 0-15 parts by weight of polyvinyl butyral resin and 100-240 parts by weight of solvent to a reactor, stirring for 1-2 hours at 40-60 DEG C, cooling to a room temperature, next, adding 40-60 parts by weight of epoxy resin and 1-5 parts by weight of hexamethylenetetramine, stirring thoroughly for dissolving, and finally, adding 0.5-5 parts by weight of nano silicon dioxide, and thoroughly dispersing and evenly stirring to obtain the low-temperature resin composition. The invention provides a low-temperature resin mixture which can be used as a support structure at minus 196 to 130 DEG C for a glass fiber cloth reinforcing material; the low-temperature resin mixture is especially applicable to low temperatures, has the characteristics of high strength, good toughness, not easy cracking and the like at low temperatures, and is excellent in product properties and high in practicability.
Description
Technical field
The invention belongs to composition and preparation thereof containing organic high molecular compound, relate to a kind of low-temperature resins composition and method of making the same of the phenolic aldehyde-epoxy containing polyester (or polyester and polyvinyl butyral acetal).Resin combination prepared by the present invention is applicable to the preparation of low temperature composite product, is particularly suitable at-196 DEG C～130 DEG C, using as the glasscloth supporting material of supporting structure the preparation method of low-temperature resins composition.
Background technology
Low temperature structure material fibre reinforced composites are the transports such as liquid Sweet natural gas, nitrogen, hydrogen, helium, storage, use key structure and the propping material of under the structure of low temperature liquid canned container manufacture and propping material and low temperature, working, the low temperature liquid canned container that employing matrix material is made is compared with the low temperature liquid canned container of ordinary metallic material, and container weight can alleviate 20%～40%.
In recent years, high-strength light fibre reinforced epoxy resin composite was applied gradually in ultra-low temperature surroundings.In the prior art, the systematic study such as Fumio Sawa epoxy resin molecular designing used under low temperature.In Formulaion of epoxy resin design, tend to encounter fragility technical problem too high, easy to crack.
Summary of the invention
Object of the present invention is intended to overcome above-mentioned deficiency of the prior art, and a kind of low-temperature resins composition and method of making the same is provided.Strengthen lamination (volume) goods poor toughness, shortcoming easy to crack at low temperatures thereby overcome existing epoxy (or phenolic aldehyde epoxy) resin glass cloth, provide one to prepare to work glasscloth enhancing lamination (volume) goods low-temperature resins composition and method of making the same at-196 DEG C～130 DEG C.
Content of the present invention is: a kind of low-temperature resins composition, is characterized in that: this resin combination is mainly made up of hexamethylenetetramine and 0.5～5 mass parts nano silicon of 15 mass parts low molecular weight polyester resins, 30～50 mass parts linear phenolic resins, 100～240 mass parts solvents, 40～60 mass parts epoxy resin, 1～5 mass parts;
Described low-molecular-weight polyester is polyethylene terephthalate, Poly(Trimethylene Terephthalate) or the polybutylene terephthalate of weight-average molecular weight 800～1200;
Described linear phenolic resin can be used any novolac resin;
Described solvent is that mass ratio is acetone: toluene: the mixture of ethanol=3:2:5～7;
Described epoxy resin is bisphenol A-type glycidyl ether epoxy.
In content of the present invention: can also be added with 1～15 mass parts polyvinyl butyral resin in described resin combination;
Described polyvinyl butyral resin is the polyvinyl butyral resin of fourth aldehyde group content (mass percentage content) 68%～82%, hydroxy radical content (mass percentage content) 17%～20.5%.
In content of the present invention: described acetone can replace with butanone or ethyl acetate.
Another content of the present invention is: a kind of preparation method of low-temperature resins composition, is characterized in that:
15 mass parts low molecular weight polyester resins, 30～50 mass parts linear phenolic resins and 100～240 mass parts solvents are joined in reactor, stir 1～2h at 40 DEG C～60 DEG C, be cooled to room temperature, add again the hexamethylenetetramine of 40～60 mass parts epoxy resin and 1～5 mass parts, fully stirring and dissolving, finally add 0.5～5 mass parts nano silicon, stir through abundant dispersion, make low-temperature resins composition;
Described low-molecular-weight polyester is polyethylene terephthalate, Poly(Trimethylene Terephthalate) or the polybutylene terephthalate of weight-average molecular weight 800～1200;
Described linear phenolic resin can be used any novolac resin;
Described solvent is that mass ratio is acetone: toluene: the mixture of ethanol=3:2:5～7;
Described epoxy resin is bisphenol A-type glycidyl ether epoxy.
In another content of the present invention: described 15 mass parts low molecular weight polyester resins, 30～50 mass parts linear phenolic resins and 100～240 mass parts solvents are joined in reactor, can replace with: 15 mass parts low molecular weight polyester resins, 30～50 mass parts linear phenolic resins, 1～15 mass parts polyvinyl butyral resin and 100～240 mass parts solvents are joined in reactor;
Described polyvinyl butyral resin is the polyvinyl butyral resin of fourth aldehyde group content (mass percentage content) 68%～82%, hydroxy radical content (mass percentage content) 17%～20.5%.
In another content of the present invention: described acetone can replace with butanone or ethyl acetate.
In content of the present invention and another content: described each component raw material is commercially available prod; Described low-molecular-weight polyester can adopt polyethylene terephthalate, Poly(Trimethylene Terephthalate) or the polybutylene terephthalate hydrolysis that Chemical market is sold to obtain, or, terephthalic acid synthetic with terephthalic acid and ethylene glycol and propylene glycol synthesizes or terephthalic acid and butyleneglycol synthesize; Any novolac resin or self-control that described linear phenolic resin can be sold by Chemical market; Fourth aldehyde group content (the mass percentage content that described polyvinyl butyral resin can use chemical plant, Changchun, Taiwan, Qingdao Haocheng Industrial Co., Ltd., Shanghai Si Xi Chemical Co., Ltd. to produce, same afterwards) 68%～82%, the product that hydroxy radical content is 17%～20.5%; Described epoxy resin is bisphenol A-type glycidyl ether epoxy, and the E-44 that can produce with Yueyang Ba Ling petro-chemical corporation, the E-44 that Xingchen Synthetic Matrials Co., Ltd., Nantong produces, the YN1826 that Jiangsu Yangnong Kumho Chemical Co., Ltd. produces, also can make by oneself; Described nano silicon, can converge the product that smart Ya Na meter novel material company limited produces with Shanghai.
Compared with prior art, the present invention has following feature and beneficial effect:
(1) the invention provides a kind of preparation method that can use low-temperature resins composition at-196 DEG C～130 DEG C as the glasscloth supporting material of supporting structure; Through retrieval, in prior art, have no and adopt pertinent literature or the report for the preparation of the liquid canned container of working under low temperature environment, structural part containing polyester (or polyester and polyvinyl butyral acetal), phenolic aldehyde and epoxy hybrid resin glass fibre reinforced composion;
(2) the cured article cross-linking density of normal conditions resol and epoxy resin is higher, and intramolecule rotation difficulty, causes fragility to increase, especially obvious under low temperature, in addition be subject to for a long time that hot and cold alternately and the interaction of external impacts the tiny flaw of material internal and trickle crackle easily expansion cause cracking, thermal stresses and mechanical stress that outside temperature sharply changes generation also easily crack, and cause cracking, in the application of low-temperature resins composition of the present invention, sheet material compressive strength is 630～840MPa, sheet material shock strength (simply supported beam, non-notch) 274～398kJ/m
2, bar/tubing compressive strength is 268～375MPa, and bar/tubing shock strength (simply supported beam, non-notch) is 186～302kJ/m
2, low-temperature resins composition temperature use range be-196～130 DEG C, the application result of embodiment also shows: the present invention introduces the lower molecular weight poly terephthalic acid second (or third of formula ratio in phenolic aldehyde-epoxy-resin systems, fourth) diol ester or and polyvinyl butyral resin long chain active molecule reduce the cross-linking density of its cured article, on the basis of proof strength, increase cured article shock-resistance, the introducing of simultaneously a small amount of nano silicon, now the coefficient of expansion of material is mainly determined by interface, the interfacial layer of filler and matrix can effectively stop the speed of expansion of matrix, thereby can play the effect that reduces shrinking percentage in resin curing process and coefficient of linear expansion, nano silicon produces stress concentration in the distortion of material, causes particle resin matrix surrender around, thereby absorbs a large amount of deformation work, hinders and the expansion of passivation crazing in resin, plays the effect that prevents destructive cracking, the non-ligating atom in nano molecular surface is more, has increased matrix and is combined with the interface of particle thereby can be combined with epoxy resin generation physical chemistry, has strengthened toughness and has improved again resistance to cracking,
(3) the present invention is specially adapted to use under low temperature, has under low temperature intensity high, and good toughness is not easy to crack; Product preparation process of the present invention is simple, easily operation, and product performance are good, practical.
Embodiment
Embodiment given below intends 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.
The preparation of first part's composition that for low temperature, polyester, phenolic aldehyde and epoxy are matrix resin
Basic raw material:
Low molecular weight polyester resin is polyethylene terephthalate, Poly(Trimethylene Terephthalate) or the polybutylene terephthalate of homemade weight-average molecular weight 800～1200; linear phenolic resin is homemade; polyvinyl butyral resin is polyvinyl butyral resin (the fourth aldehyde group content 68%～82% that Shanghai Si Xi Chemical Co., Ltd. produces; hydroxy radical content is 17%～20.5%); epoxy resin is the E-44 that Yueyang Ba Ling petro-chemical corporation produces, and nano silicon is that the nano silicon that smart Ya Na meter novel material company limited produces is converged in Shanghai.
Embodiment 1-1:
The polyethylene terephthalate of 15 ㎏ weight-average molecular weight 800,45 ㎏ linear phenolic resins and 210 ㎏ solvents (mass ratio is acetone: toluene: ethanol=3:2:6) are joined in reactor, stir 1～2h at 40 DEG C～60 DEG C, be cooled to room temperature and add 45 ㎏ epoxy resin and 1 ㎏ hexamethylenetetramine, fully stirring and dissolving, finally add 0.5 ㎏ nano silicon, stir through abundant dispersion, make low-temperature resins composition.
Embodiment 1-2:
The polyethylene terephthalate of 15 ㎏ weight-average molecular weight 900,30 ㎏ linear phenolic resins and 100 ㎏ solvents (mass ratio is butanone: toluene: ethanol=3:2:5) are joined in reactor, stir 1～2h at 40 DEG C～60 DEG C, be cooled to room temperature and add 55 ㎏ epoxy resin and 5 ㎏ hexamethylenetetramines, fully stirring and dissolving, finally add 3.5 ㎏ nano silicons, stir through abundant dispersion, make low-temperature resins composition.
Embodiment 1-3:
The polyethylene terephthalate of 15 ㎏ weight-average molecular weight 1000,40 ㎏ linear phenolic resins and 150 ㎏ solvents (mass ratio is ethyl acetate: toluene: ethanol=3:2:6) are joined in reactor, stir 1～2h at 40 DEG C～60 DEG C, be cooled to room temperature and add 40 ㎏ epoxy resin and 2 ㎏ hexamethylenetetramines, fully stirring and dissolving, finally add 1.5 ㎏ nano silicons, stir through abundant dispersion, make low-temperature resins composition.
Embodiment 1-4:
The polyethylene terephthalate of 15 ㎏ weight-average molecular weight 1100,30 ㎏ linear phenolic resins, 1 ㎏ polyvinyl butyral resin and 100 ㎏ solvents (mass ratio is ethyl acetate: toluene: ethanol=3:2:7) are joined in reactor, stir 1～2h at 40 DEG C～60 DEG C, be cooled to room temperature and add 40 ㎏ epoxy resin and 2 ㎏ hexamethylenetetramines, fully stirring and dissolving, finally add 1.5 ㎏ nano silicons, stir through abundant dispersion, make low-temperature resins composition.
Embodiment 1-5:
The polyethylene terephthalate of 15 ㎏ weight-average molecular weight 1200,40 ㎏ linear phenolic resins, 7 ㎏ polyvinyl butyral resins and 240 ㎏ solvents (mass ratio is ethyl acetate: toluene: ethanol=3:2:5.5) are joined in reactor, stir 1～2h at 40 DEG C～60 DEG C, be cooled to room temperature and add 60 ㎏ epoxy resin and 2 ㎏ hexamethylenetetramines, fully stirring and dissolving, finally add 1.5 ㎏ nano silicons, stir through abundant dispersion, make low-temperature resins composition.
Embodiment 1-6:
The polyethylene terephthalate of 15 ㎏ weight-average molecular weight 1200,50 ㎏ linear phenolic resins, 15 ㎏ polyvinyl butyral resins and 180 ㎏ solvents (mass ratio is ethyl acetate: toluene: ethanol=3:2:6.5) are joined in reactor, stir 1～2h at 40 DEG C～60 DEG C, be cooled to room temperature and add 40 ㎏ epoxy resin and 2 ㎏ hexamethylenetetramines, fully stirring and dissolving, finally add 1.5 ㎏ nano silicons, stir through abundant dispersion, make low-temperature resins composition.
Embodiment 1-7:
The Poly(Trimethylene Terephthalate) of 15 ㎏ weight-average molecular weight 1200,50 ㎏ linear phenolic resins and 240 ㎏ solvents (mass ratio is acetone: toluene: ethanol=3:2:7) are joined in reactor, stir 1～2h at 40 DEG C～60 DEG C, be cooled to room temperature and add 50 ㎏ epoxy resin and 3 ㎏ hexamethylenetetramines, fully stirring and dissolving, finally add 2.5 ㎏ nano silicons, stir through abundant dispersion, make low-temperature resins composition.
Embodiment 1-8:
The Poly(Trimethylene Terephthalate) of 15 ㎏ weight-average molecular weight 800,35 ㎏ linear phenolic resins and 160 ㎏ solvents (mass ratio is ethyl acetate: toluene: ethanol=3:2:5) are joined in reactor, stir 1～2h at 40 DEG C～60 DEG C, be cooled to room temperature and add 45 ㎏ epoxy resin and 4 ㎏ hexamethylenetetramines, fully stirring and dissolving, finally add 4 ㎏ nano silicons, stir through abundant dispersion, make low-temperature resins composition.
Embodiment 1-9:
The Poly(Trimethylene Terephthalate) of 15 ㎏ weight-average molecular weight 1000,35 ㎏ linear phenolic resins, 1 ㎏ polyvinyl butyral resin and 100 ㎏ solvents (mass ratio is ethyl acetate: toluene: ethanol=3:2:5) are joined in reactor, stir 1～2h at 40 DEG C～60 DEG C, be cooled to room temperature and add 55 ㎏ epoxy resin and 1 ㎏ hexamethylenetetramine, fully stirring and dissolving, finally add 0.5 ㎏ nano silicon, stir through abundant dispersion, make low-temperature resins composition.
Embodiment 1-10:
The Poly(Trimethylene Terephthalate) of 15 ㎏ weight-average molecular weight 1200,45 ㎏ linear phenolic resins, 5 ㎏ polyvinyl butyral resins and 140 ㎏ solvents (mass ratio is acetone: toluene: ethanol=3:2:6) are joined in reactor, stir 1～2h at 40 DEG C～60 DEG C, be cooled to room temperature and add 40 ㎏ epoxy resin and 4 ㎏ hexamethylenetetramines, fully stirring and dissolving, finally add 1.5 ㎏ nano silicons, stir through abundant dispersion, make low-temperature resins composition.
Embodiment 1-11:
The Poly(Trimethylene Terephthalate) of 15 ㎏ weight-average molecular weight 900,30 ㎏ linear phenolic resins, 15 ㎏ polyvinyl butyral resins and 210 ㎏ solvents (mass ratio is acetone: toluene: ethanol=3:2:6.5) are joined in reactor, stir 1～2h at 40 DEG C～60 DEG C, be cooled to room temperature and add 60 ㎏ epoxy resin and 2 ㎏ hexamethylenetetramines, fully stirring and dissolving, finally add 3.5 ㎏ nano silicons, stir through abundant dispersion, make low-temperature resins composition.
Embodiment 1-12:
The Poly(Trimethylene Terephthalate) of 15 ㎏ weight-average molecular weight 1100,40 ㎏ linear phenolic resins and 160 ㎏ solvents (mass ratio is acetone: toluene: ethanol=3:2:5.5) are joined in reactor, stir 1～2h at 40 DEG C～60 DEG C, be cooled to room temperature and add 50 ㎏ epoxy resin and 4 ㎏ hexamethylenetetramines, fully stirring and dissolving, finally add 5 ㎏ nano silicons, stir through abundant dispersion, make low-temperature resins composition.
Embodiment 1-13:
The polybutylene terephthalate of 15 ㎏ weight-average molecular weight 800,30 ㎏ linear phenolic resins and 180 ㎏ solvents (mass ratio is ethyl acetate: toluene: ethanol=3:2:7) are joined in reactor, stir 1～2h at 40 DEG C～60 DEG C, be cooled to room temperature and add 50 ㎏ epoxy resin and 2 ㎏ hexamethylenetetramines, fully stirring and dissolving, finally add 1.5 ㎏ nano silicons, stir through abundant dispersion, make low-temperature resins composition.
Embodiment 1-14:
The polybutylene terephthalate of 15 ㎏ weight-average molecular weight 1000,50 ㎏ linear phenolic resins, 12 ㎏ polyvinyl butyral resins and 240 ㎏ solvents (mass ratio is butanone: toluene: ethanol=3:2:6.5) are joined in reactor, stir 1～2h at 40 DEG C～60 DEG C, be cooled to room temperature and add 45 ㎏ epoxy resin and 5 ㎏ hexamethylenetetramines, fully stirring and dissolving, finally add 4.5 ㎏ nano silicons, stir through abundant dispersion, make low-temperature resins composition.
Embodiment 1-15:
The polybutylene terephthalate of 15 ㎏ weight-average molecular weight 1200,40 ㎏ linear phenolic resins, 8 ㎏ polyvinyl butyral resins and 200 ㎏ solvents (mass ratio is acetone: toluene: ethanol=3:2:5) are joined in reactor, stir 1～2h at 40 DEG C～60 DEG C, be cooled to room temperature and add 55 ㎏ epoxy resin and 3 ㎏ hexamethylenetetramines, fully stirring and dissolving, finally add 3.5 ㎏ nano silicons, stir through abundant dispersion, make low-temperature resins composition.
Embodiment 1-16:
The polybutylene terephthalate of 15 ㎏ weight-average molecular weight 1000,50 ㎏ linear phenolic resins and 240 ㎏ solvents (mass ratio is acetone: toluene: ethanol=3:2:6.5) are joined in reactor, stir 1～2h at 40 DEG C～60 DEG C, be cooled to room temperature and add 40 ㎏ epoxy resin and 5 ㎏ hexamethylenetetramines, fully stirring and dissolving, finally add 0.5 ㎏ nano silicon, stir through abundant dispersion, make low-temperature resins composition.
Embodiment 1-17:
The polybutylene terephthalate of 15 ㎏ weight-average molecular weight 900,40 ㎏ linear phenolic resins and 200 ㎏ solvents (mass ratio is acetone: toluene: ethanol=3:2:7) are joined in reactor, stir 1～2h at 40 DEG C～60 DEG C, be cooled to room temperature and add 60 ㎏ epoxy resin and 1 ㎏ hexamethylenetetramine, fully stirring and dissolving, finally add 5 ㎏ nano silicons, stir through abundant dispersion, make low-temperature resins composition.
Embodiment 1-18:
The polybutylene terephthalate of 15 ㎏ weight-average molecular weight 1100,30 ㎏ linear phenolic resins and 100 ㎏ solvents (mass ratio is acetone: toluene: ethanol=3:2:5) are joined in reactor, stir 1～2h at 40 DEG C～60 DEG C, be cooled to room temperature and add 50 ㎏ epoxy resin and 1 ㎏ hexamethylenetetramine, fully stirring and dissolving, finally add 2.5 ㎏ nano silicons, stir through abundant dispersion, make low-temperature resins composition.
The application of second section low-temperature resins composition
Adopt the made low-temperature resins composition of above-described embodiment 1-1～1-18 and commercially available glasscloth, the resistance to low temperature situation that rolls the veneer sheet, tubing and the bar that obtain by high temperature hot pressing machine lamination or high temperature sees the following form:
Adopt the resistance to low temperature information slip of the obtained veneer sheet of embodiment 1-1～1-18 product
Embodiment 2:
A kind of low-temperature resins composition, this resin combination is made up of hexamethylenetetramine and the 0.5 mass parts nano silicon of 15 mass parts low molecular weight polyester resins, 30 mass parts linear phenolic resins, 100 mass parts solvents, 40 mass parts epoxy resin, 1 mass parts.
Embodiment 3:
A kind of low-temperature resins composition, this resin combination is made up of hexamethylenetetramine and the 5 mass parts nano silicons of 15 mass parts low molecular weight polyester resins, 50 mass parts linear phenolic resins, 240 mass parts solvents, 60 mass parts epoxy resin, 5 mass parts.
Embodiment 4:
A kind of low-temperature resins composition, this resin combination is made up of hexamethylenetetramine and the 2.7 mass parts nano silicons of 15 mass parts low molecular weight polyester resins, 40 mass parts linear phenolic resins, 170 mass parts solvents, 50 mass parts epoxy resin, 3 mass parts.
Embodiment 5～11:
A kind of low-temperature resins composition, this resin combination is made up of hexamethylenetetramine and 0.5～5 mass parts nano silicon of 15 mass parts low molecular weight polyester resins, 30～50 mass parts linear phenolic resins, 100～240 mass parts solvents, 40～60 mass parts epoxy resin, 1～5 mass parts.
Each component in embodiment 5～11 and mass parts consumption (unit can be: gram) see the following form:
Embodiment 12～21:
A kind of low-temperature resins composition, this resin combination is also added with 1～15 mass parts polyvinyl butyral resin; Concrete addition in embodiment 2～11 is 1,3,5,7,8,9,10,11,13,15 mass parts;
Described polyvinyl butyral resin is the polyvinyl butyral resin of fourth aldehyde group content (mass percentage content) 68%～82%, hydroxy radical content (mass percentage content) 17%～20.5%.
Embodiment 22:
A kind of preparation method of low-temperature resins composition, step is: low molecular weight polyester resin, linear phenolic resin and solvent are joined in reactor, stir 1～2h at 40 DEG C～60 DEG C, be cooled to room temperature, add epoxy resin and hexamethylenetetramine, fully stirring and dissolving, finally adds nano silicon again, stir through abundant dispersion, make low-temperature resins composition;
The concrete consumption (mass parts) of each component raw material can be with arbitrary in embodiment 2～11.
Embodiment 23:
A kind of preparation method of low-temperature resins composition, described low molecular weight polyester resin, linear phenolic resin and solvent are joined in reactor, replace with: low molecular weight polyester resin, linear phenolic resin, polyvinyl butyral resin and solvent are joined in reactor; The concrete consumption (mass parts) of each component raw material can be with arbitrary in embodiment 12～21.
Described polyvinyl butyral resin is the polyvinyl butyral resin of fourth aldehyde group content (mass percentage content) 68%～82%, hydroxy radical content (mass percentage content) 17%～20.5%.
In above-described embodiment 2～21: described low-molecular-weight polyester is polyethylene terephthalate, Poly(Trimethylene Terephthalate) or the polybutylene terephthalate of weight-average molecular weight 800～1200; Described linear phenolic resin can be used any novolac resin; Described solvent is that mass ratio is acetone (acetone can replace with butanone or ethyl acetate): toluene: the mixture of ethanol=3:2:5～7; Described epoxy resin is bisphenol A-type glycidyl ether epoxy.
In above-described embodiment 2～21: described each component raw material is commercially available prod; Described low-molecular-weight polyester can adopt polyethylene terephthalate, Poly(Trimethylene Terephthalate) or the polybutylene terephthalate hydrolysis that Chemical market is sold to obtain, or, terephthalic acid synthetic with terephthalic acid and ethylene glycol and propylene glycol synthesizes or terephthalic acid and butyleneglycol synthesize; Any novolac resin or self-control that described linear phenolic resin can be sold by Chemical market; Fourth aldehyde group content (the mass percentage content that described polyvinyl butyral resin can use chemical plant, Changchun, Taiwan, Qingdao Haocheng Industrial Co., Ltd., Shanghai Si Xi Chemical Co., Ltd. to produce, same afterwards) 68%～82%, the product that hydroxy radical content is 17%～20.5%; Described epoxy resin is bisphenol A-type glycidyl ether epoxy, and the E-44 that can produce with Yueyang Ba Ling petro-chemical corporation, the E-44 that Xingchen Synthetic Matrials Co., Ltd., Nantong produces, the YN1826 that Jiangsu Yangnong Kumho Chemical Co., Ltd. produces, also can make by oneself; Described nano silicon, can converge the product that smart Ya Na meter novel material company limited produces with Shanghai.
In above-described embodiment: in the percentage adopting, do not indicate especially, be quality (weight) percentage; In the ratio adopting, do not indicate especially, be quality (weight) ratio; Described weight part can be all gram or kilogram.
In above-described embodiment: processing parameter (temperature, time, concentration etc.) and each amounts of components numerical value etc. in each step is scope, and any point is all applicable.
The not concrete same prior art of technology contents of narrating 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 and have described good result described in content of the present invention.
Claims (6)
1. a low-temperature resins composition, is characterized in that: this resin combination is mainly made up of hexamethylenetetramine and 0.5～5 mass parts nano silicon of 15 mass parts low molecular weight polyester resins, 30～50 mass parts linear phenolic resins, 100～240 mass parts solvents, 40～60 mass parts epoxy resin, 1～5 mass parts;
Described low-molecular-weight polyester is polyethylene terephthalate, Poly(Trimethylene Terephthalate) or the polybutylene terephthalate of weight-average molecular weight 800～1200;
Described solvent is that mass ratio is acetone: toluene: the mixture of ethanol=3:2:5～7;
Described epoxy resin is bisphenol A-type glycidyl ether epoxy.
2. by low-temperature resins composition claimed in claim 1, it is characterized in that: in described resin combination, be also added with 1～15 mass parts polyvinyl butyral resin;
Described polyvinyl butyral resin is the polyvinyl butyral resin of fourth aldehyde group content 68%～82%, hydroxy radical content 17%～20.5%.
3. by the low-temperature resins composition described in claim 1 or 2, it is characterized in that: described acetone replaces with butanone or ethyl acetate.
4. a preparation method for low-temperature resins composition, is characterized in that:
15 mass parts low molecular weight polyester resins, 30～50 mass parts linear phenolic resins and 100～240 mass parts solvents are joined in reactor, stir 1～2h at 40 DEG C～60 DEG C, be cooled to room temperature, add again the hexamethylenetetramine of 40～60 mass parts epoxy resin and 1～5 mass parts, stirring and dissolving, finally add 0.5～5 mass parts nano silicon, stir, make low-temperature resins composition;
Described low-molecular-weight polyester is polyethylene terephthalate, Poly(Trimethylene Terephthalate) or the polybutylene terephthalate of weight-average molecular weight 800～1200;
Described solvent is that mass ratio is acetone: toluene: the mixture of ethanol=3:2:5～7;
Described epoxy resin is bisphenol A-type glycidyl ether epoxy.
5. by the preparation method of low-temperature resins composition claimed in claim 4, it is characterized in that: described 15 mass parts low molecular weight polyester resins, 30～50 mass parts linear phenolic resins and 100～240 mass parts solvents are joined in reactor and replaced with: 15 mass parts low molecular weight polyester resins, 30～50 mass parts linear phenolic resins, 1～15 mass parts polyvinyl butyral resin and 100～240 mass parts solvents are joined in reactor;
Described polyvinyl butyral resin is the polyvinyl butyral resin of fourth aldehyde group content 68%～82%, hydroxy radical content 17%～20.5%.
6. by the preparation method of the low-temperature resins composition described in claim 4 or 5, it is characterized in that: described acetone replaces with butanone or ethyl acetate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410145795.5A CN103937162B (en) | 2014-04-11 | 2014-04-11 | Low-temperature resins compositions and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410145795.5A CN103937162B (en) | 2014-04-11 | 2014-04-11 | Low-temperature resins compositions and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103937162A true CN103937162A (en) | 2014-07-23 |
| CN103937162B CN103937162B (en) | 2016-08-17 |
Family
ID=51185054
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410145795.5A Active CN103937162B (en) | 2014-04-11 | 2014-04-11 | Low-temperature resins compositions and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103937162B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104449264A (en) * | 2014-12-19 | 2015-03-25 | 四川东材科技集团股份有限公司 | Low-temperature rapid-curing impregnating resin for glass-fiber-clad conductor and preparation method thereof |
| CN106047270A (en) * | 2016-05-26 | 2016-10-26 | 合肥市田源精铸有限公司 | Metal adhesive applicable to low temperatures and preparation method therefor |
| CN106243714A (en) * | 2016-07-29 | 2016-12-21 | 安徽科邦树脂科技有限公司 | A kind of cold-resistant synthetic resin and preparation method thereof |
| CN106751432A (en) * | 2016-12-22 | 2017-05-31 | 苏州缔绿电子科技有限公司 | A kind of low-temperature-resistance high-toughness composite and preparation method thereof |
| CN109251474A (en) * | 2018-10-24 | 2019-01-22 | 南京拉艾夫医药科技有限公司 | Preservation container for Pidotimod dry suspension |
| CN109354835A (en) * | 2018-10-24 | 2019-02-19 | 南京拉艾夫医药科技有限公司 | It is a kind of for erythromycin lactobionate freeze-drying after preservation cryo-conservation material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001026720A (en) * | 1999-05-13 | 2001-01-30 | Toray Ind Inc | Resin composition for fiber-reinforced composite material, prepreg and fiber-reinforced composite material |
| CN101456945A (en) * | 2008-12-24 | 2009-06-17 | 郭立耀 | Method for producing low molecular weight polyester plasticiser |
| CN101457011A (en) * | 2007-12-12 | 2009-06-17 | 深圳大学 | Preparation of composite nano particle modified epoxy resin |
| CN102603999A (en) * | 2012-03-23 | 2012-07-25 | 开封市鑫源有机化工厂 | Method for modifying unsaturated polyester/epoxy resin block copolymer by in-situ polymerization of nanometer silicon dioxide |
-
2014
- 2014-04-11 CN CN201410145795.5A patent/CN103937162B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001026720A (en) * | 1999-05-13 | 2001-01-30 | Toray Ind Inc | Resin composition for fiber-reinforced composite material, prepreg and fiber-reinforced composite material |
| CN101457011A (en) * | 2007-12-12 | 2009-06-17 | 深圳大学 | Preparation of composite nano particle modified epoxy resin |
| CN101456945A (en) * | 2008-12-24 | 2009-06-17 | 郭立耀 | Method for producing low molecular weight polyester plasticiser |
| CN102603999A (en) * | 2012-03-23 | 2012-07-25 | 开封市鑫源有机化工厂 | Method for modifying unsaturated polyester/epoxy resin block copolymer by in-situ polymerization of nanometer silicon dioxide |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104449264A (en) * | 2014-12-19 | 2015-03-25 | 四川东材科技集团股份有限公司 | Low-temperature rapid-curing impregnating resin for glass-fiber-clad conductor and preparation method thereof |
| CN104449264B (en) * | 2014-12-19 | 2017-02-22 | 四川东材科技集团股份有限公司 | Low-temperature rapid-curing impregnating resin for glass-fiber-clad conductor and preparation method thereof |
| CN106047270A (en) * | 2016-05-26 | 2016-10-26 | 合肥市田源精铸有限公司 | Metal adhesive applicable to low temperatures and preparation method therefor |
| CN106243714A (en) * | 2016-07-29 | 2016-12-21 | 安徽科邦树脂科技有限公司 | A kind of cold-resistant synthetic resin and preparation method thereof |
| CN106751432A (en) * | 2016-12-22 | 2017-05-31 | 苏州缔绿电子科技有限公司 | A kind of low-temperature-resistance high-toughness composite and preparation method thereof |
| CN109251474A (en) * | 2018-10-24 | 2019-01-22 | 南京拉艾夫医药科技有限公司 | Preservation container for Pidotimod dry suspension |
| CN109354835A (en) * | 2018-10-24 | 2019-02-19 | 南京拉艾夫医药科技有限公司 | It is a kind of for erythromycin lactobionate freeze-drying after preservation cryo-conservation material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103937162B (en) | 2016-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103937162A (en) | Low-temperature resin composition and preparation method thereof | |
| Capricho et al. | Multifunctionality in epoxy resins | |
| US3686359A (en) | Curable polyepoxide compositions | |
| CN103093896B (en) | A kind of manufacture method of carbon fiber composite material cable wire | |
| CN102040802A (en) | Epoxy resin system and application thereof | |
| CN102020831A (en) | Composite material for wind power generation blades | |
| CN103937152B (en) | Polyester-phenolic aldehyde-epoxy composite material and preparation method thereof | |
| CN105219027A (en) | Epoxy-resin systems and preparation method thereof | |
| CN102040805A (en) | Epoxy resin system for manufacturing blade mould of wind-driven generator and preparation method thereof | |
| Derradji et al. | Cost effective surface‐modified basalt fibers‐reinforced phthalonitrile composites with improved mechanical properties and advanced nuclear shielding efficiency | |
| CN103265926A (en) | Composite nano powder modified imine epoxy adhesive | |
| CN103935092B (en) | Polyester-phenolic aldehyde-polyvinyl butyral resin-epoxy composite material and preparation method thereof | |
| CN102627930A (en) | Epoxy structural adhesive for wind wheel blades and its preparation method | |
| CN107778774B (en) | Epoxy resin adhesive film and preparation method thereof | |
| CN104045978A (en) | Polyarylether nitrile/epoxy resin copolymerized modified composition and preparation method and application thereof | |
| CN103093888B (en) | A kind of carbon fiber composite cable core | |
| CN101735570A (en) | Epoxy resin system used for blades of wind driven generator and modification method thereof | |
| Qian et al. | Improvement in alkali‐resistance of basalt fiber‐reinforced polymer by Ti3C2TX (MXene) modified matrix | |
| Badyankal et al. | Realization of mechanical and tribological properties of hybrid banana, sisal, and pineapple fiber epoxy composites using naturally available fillers | |
| JP2011148911A (en) | Large-sized molding resin composition | |
| Varley et al. | Effect of aromatic substitution on the cure reaction and network properties of anhydride cured triphenyl ether tetraglycidyl epoxy resins | |
| JP5521572B2 (en) | Resin composition for syntactic foam | |
| CN101805442A (en) | Epoxy resin composition for large wind blades and preparation method thereof | |
| CN105199092A (en) | Preparation method of alicyclic epoxy resin hyperbranched polyester flexibilizer for mutual inductors | |
| CN111218110B (en) | Cyanate ester matrix resin and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |