CN103435988B - High-temperature resistant unsaturated polyester resin system and preparation method thereof - Google Patents
High-temperature resistant unsaturated polyester resin system and preparation method thereof Download PDFInfo
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- CN103435988B CN103435988B CN201310412881.3A CN201310412881A CN103435988B CN 103435988 B CN103435988 B CN 103435988B CN 201310412881 A CN201310412881 A CN 201310412881A CN 103435988 B CN103435988 B CN 103435988B
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Abstract
The invention relates to a high-temperature resistant unsaturated polyester resin system, comprising the following materials in parts by weight: 100 parts of unsaturated polyester resin and 1-100 parts of phenyl acetylene silane resin. According to the high-temperature resistant unsaturated polyester resin system provided by the invention, the phenyl acetylene silane resin is dissolved into the unsaturated polyester resin by adopting a physical blending method, so as to obtain a phenyl acetylene silane resin-modified unsaturated polyester resin system after being completely dissolved. The phenyl acetylene silane-modified unsaturated polyester resin prepared by the preparation method has excellent heat-resistant quality and thermal oxidation performance, and good mechanical property and dielectric property, and has an extremely broad application prospect in the high-end fields such as national defense, aviation, aerospace and the like.
Description
Technical field
The present invention relates to polymeric material field, particularly relate to phenylacetylene base silane modified unsaturated polyester resin and preparation method thereof.
Background technology
Unsaturated polyester (UP) is by the saturated simple linear polymer generated through polycondensation with unsaturated dibasic acid (or acid anhydrides) and dibasic alcohol, containing non-aromatic unsaturated link(age) in its molecular structure, cause crosslinking reaction by suitable initiator and form a kind of thermosetting material.The relative density of unsaturated polyester resin is about 1.11 ~ 1.20, and during solidification, volumetric shrinkage is larger.Processing performance is excellent is the maximum advantage of unsaturated polyester resin, can at room temperature solidify, normal pressure compacted under, and processing performance is flexible, is particularly suitable for large-scale and making in site glass fiber reinforced plastics product; Resin good combination property after solidification, mechanical performance index a little less than epoxy resin, but is better than resol.Erosion resistance, electrical property and flame retardant resistance can by selecting the resin of the suitable trade mark to meet the demands, and color of resin is shallow, can make transparent article; And wide in variety, scalable, price is lower.
Using unsaturated polyester as the glass fiber reinforced plastics composite material of matrix resin, be widely used in automobile, building, electrically and the industry such as daily necessities owing to having higher mechanical property, good resistance to chemical attack, weathering resistance and lower cost.But unsaturated polyester resin resistance toheat is poor, heat-drawn wire is 50 ~ 60 DEG C, therefore needs to carry out modification to it, to meet the application of unsaturated polyester resin in high temperature resistant field.
Improve unsaturated polyester resin thermotolerance at present both at home and abroad and generally have following methods:
(1) adopt high-performance matrix resin to unsaturated polyester resin modification
Epoxy resin, silicone resin, bimaleimide resin, cyanate ester resin and polyimide resin etc. is such as used to carry out modification.Such as CN103183945A discloses a kind of modified unsaturated polyester resin and preparation method thereof, comprise following component and weight part content: unsaturated polyester resin 100, toughened resin 8-10, epoxy resin 18-20, promotor 0.7-1, mill base 0.7-1, solidifying agent 0.8-1, in unsaturated polyester resin, add toughened resin, epoxy resin, promotor and mill base successively stir, then place deaeration, vacuumize, after exhausting vacuum, add solidifying agent wherein, continue to stir and vacuumize, obtaining modified unsaturated polyester resin.
(2) in unsaturated polyester resin, second-phase material is added
In unsaturated polyester resin, add rigid particles such as nanometer silicon dioxide particle also can improve the thermotolerance of unsaturated polyester resin.As CN102617805A discloses a kind of reacting nano SiO
2the method of in-situ polymerization modified unsaturated polyester resin.Dibasic alcohol, diprotic acid are joined in polymerization reactor and reacted, and when system acid number is 10-50mgKOH/g, reaction terminates, and lowers the temperature and adds stopper, paraffin, linking agent; Described reacting nano SiO
2belong to the nano silicon of in-situ surface finishing, its different times in polyreaction is added.
And phenylacetylene base silane is as a kind of novel silicone resin, be characterized in molecule containing Si-C key and C ≡ C key, crosslinking curing is carried out in reaction by intramolecule active group, and this kind of material has the processing characteristics of general polymer, excellent resistance to elevated temperatures, dielectric properties and mechanical property and is applied to the high-end fields such as aerospace.These polymkeric substance are all using carbon silicon key as the skeleton structure of molecule, and what have also contains phenyl ring.Substituting group on carbon atom and Siliciumatom is of a great variety, and comprise aryl, alkyl, hydrogen atom etc., they have the resistance toheat more much higher than common superpolymer, just day by day cause the concern of scientific research personnel.
Summary of the invention
An object of the present invention is to provide and adopts phenylacetylene base silane modified unsaturated polyester resin, prepare novel organic-inorganic hybrid resin system, to meet various advanced composite material moulding process, thus widen unsaturated polyester resin further in the high temperature resistant application waiting high-technology field.There is cross-linking and curing reaction and form tridimensional network in described hybrid systems, to reach the effect improving unsaturated polyester resin resistance toheat under the effect of light, heat or chemical initiator.
For reaching this object, the present invention adopts following technical scheme:
A kind of high temperature resistant unsaturated polyester resin system, its raw material weight number comprises: unsaturated polyester resin 100 parts, phenyl acetylene silane resin 1 ~ 100 part is such as 4 parts, 7 parts, 11 parts, 16 parts, 21 parts, 25 parts, 29 parts, 35 parts, 41 parts, 46 parts, 50 parts, 55 parts, 60 parts, 65 parts, 72 parts, 78 parts, 83 parts, 88 parts, 91 parts, 94 parts, 99 parts etc.
As optimal technical scheme, high temperature resistant unsaturated polyester resin system of the present invention, its raw material weight number comprises: unsaturated polyester resin 100 parts, phenyl acetylene silane resin 10 ~ 100 parts.
As optimal technical scheme, high temperature resistant unsaturated polyester resin system of the present invention, its raw material weight number comprises: unsaturated polyester resin 100 parts, phenyl acetylene silane resin 30 ~ 70 parts.
Phenyl acetylene silane resin has good solubility in ordinary organic solvents, can the viscosity of the effective hierarchy of control by prepolymerization reaction, is applicable to the moulding process of various advanced composite material.Ethynyl in phenyl acetylene silane resin structure has higher reactive behavior, not only can be shaping at ambient temperature, also under heat or photochemical effect, curing reaction can be completed by addition reaction, in whole solidification process, do not have volatile byproducts to produce.But the compatibility problem of two-phase that what first this kind of method will solve is, this is the key determining material property.
Phenyl acetylene silane resin has excellent heat-resisting and thermal oxidation, adopts the resistance toheat of TGA to phenyl acetylene silane resin to study, the wherein Td of methyl famesoate in nitrogen
5(decomposition temperature of mass loss 5%) is 615 DEG C, and the quality retention rate of 800 DEG C is 91.1%.Phenyl acetylene silane resin and unsaturated polyester resin have good consistency, modification can be carried out to unsaturated polyester resin by the mode of physical blending, ethynyl simultaneously in phenylacetylene base silane structure and the carbon-carbon double bond in unsaturated polyester ester structure can separately or react to each other formation three-dimensional net structure, to reach the effect of raising unsaturated polyester resin resistance toheat.
As optimal technical scheme, high temperature resistant unsaturated polyester resin system of the present invention, described phenyl acetylene silane resin is the one kind or two or more mixture in tolane base silane resin, three phenyl acetylene silane resin or four phenyl acetylene silane resin.
Shown in the structural formula as I of tolane base silane resin.
Wherein: R1, R2 are alkyl, aryl or hydrogen atom.
Shown in the structural formula as I I of three phenyl acetylene silane resin.
Wherein: R is alkyl, aryl or hydrogen atom.
Shown in the structural formula as I II of four phenyl acetylene silane resin.
An object of the present invention is also to provide the preparation method of described high temperature resistant unsaturated polyester resin system, phenyl acetylene silane resin is comprised the steps: to be dissolved in unsaturated polyester resin, until completely dissolved, described phenylacetylene silane resin modified unsaturated polyester resin system is obtained.This method is direct physical blending method.
High temperature resistant unsaturated polyester resin system preparation method of the present invention adopts physical blending, and preparation technology is simple, easy to operate.The silane-modified unsaturated polyester resin of phenylacetylene at room temperature has satisfactory stability, high temperature resistant and antioxidant property is excellent, has industrial applicibility, has extremely broad application prospect in the high-end field such as national defence, Aeronautics and Astronautics.
Embodiment
Technical scheme of the present invention is further illustrated below by embodiment.
The present invention utilizes physical blending method to prepare a kind of phenylacetylene base silane modification unsaturated polyester hybrid resin.Phenylacetylene base silane is dissolved in unsaturated polyester resin, composition of raw materials composition counts unsaturated polyester resin 100 parts by weight, phenylacetylene base silane 1 ~ 100 part, until completely dissolved, obtains a kind of phenylacetylene silane resin modified unsaturated polyester resin system.Phenyl acetylene silane resin can be tolane base silane resin, three phenyl acetylene silane resin or four phenyl acetylene silane resin.
Embodiment one
First by adjacent benzene-type unsaturated polyester resin 100 weight part, methyl famesoate resin 10 weight part carries out physical blending, until completely dissolved, prepare methyl famesoate modified unsaturated polyester hybrid resin, the heat-drawn wire of this resin system is 102 DEG C.
Embodiment two
First by metaphenylene unsaturated polyester resin 100 weight part, methyl three phenyl acetylene silane resin 25 weight part carries out physical blending, until completely dissolved, prepare the silane-modified unsaturated polyester hybrid resin of methyl three phenylacetylene base, the heat-drawn wire of this resin system is 110 DEG C.
Embodiment three
First by Bisphenol a unsaturated polyester resin 100 weight part, four phenyl acetylene silane resin 50 weight parts carry out physical blending, until completely dissolved, prepare four phenylacetylene base silane modified unsaturated polyester hybrid resins, the heat-drawn wire of this resin system is 156 DEG C.
Embodiment four
First by epoxy acrylic resin 100 weight part, methyl famesoate resin 1 weight part carries out physical blending, until completely dissolved, prepare methyl famesoate modified unsaturated polyester hybrid resin, the heat-drawn wire of this resin system is 95 DEG C.
Embodiment five
First by chloro unsaturated polyester resin 100 weight part, four phenyl acetylene silane resin 100 weight parts carry out physical blending, until completely dissolved, prepare four phenylacetylene base silane modified unsaturated polyester hybrid resins, the heat-drawn wire of this resin system is 176 DEG C.
Embodiment six
First by bromo unsaturated polyester resin 100 weight part, methyl three phenyl acetylene silane resin 75 weight part carries out physical blending, until completely dissolved, prepare the silane-modified unsaturated polyester hybrid resin of methyl three phenylacetylene base, the heat-drawn wire of this resin system is 135 DEG C.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (4)
1. a high temperature resistant unsaturated polyester resin system, is characterized in that, its raw material weight number comprises: unsaturated polyester resin 100 parts, phenyl acetylene silane resin 1 ~ 100 part; Described phenyl acetylene silane resin is the one kind or two or more mixture in tolane base silane resin, three phenyl acetylene silane resin or four phenyl acetylene silane resin, and described unsaturated polyester resin is adjacent benzene-type unsaturated polyester resin, metaphenylene unsaturated polyester resin, Bisphenol a unsaturated polyester resin, chloro unsaturated polyester resin or bromo unsaturated polyester resin.
2. high temperature resistant unsaturated polyester resin system according to claim 1, is characterized in that, its raw material weight number comprises: unsaturated polyester resin 100 parts, phenyl acetylene silane resin 10 ~ 100 parts.
3. high temperature resistant unsaturated polyester resin system according to claim 1 and 2, is characterized in that, its raw material weight number comprises: unsaturated polyester resin 100 parts, phenyl acetylene silane resin 30 ~ 70 parts.
4. the preparation method of the high temperature resistant unsaturated polyester resin system described in an any one of claim 1-3, phenyl acetylene silane resin is comprised the steps: to be dissolved in unsaturated polyester resin, until completely dissolved, described phenylacetylene silane resin modified unsaturated polyester resin system is obtained.
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| CN103435988B true CN103435988B (en) | 2015-07-01 |
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| CN104151840A (en) * | 2014-07-21 | 2014-11-19 | 华东理工大学 | Silicon-alkyne resin-modified polyborosilazane composite material and preparation method thereof |
| CN118291013B (en) * | 2024-06-05 | 2024-09-17 | 上海申茂电磁线有限公司 | Polyester enameled rectangular copper wire and preparation process thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1533878A (en) * | 2003-03-27 | 2004-10-06 | 郑光洙 | Resin ceiling and its manufacturing method |
| CN101864076A (en) * | 2010-05-14 | 2010-10-20 | 华东理工大学 | Cyanate resin modified by phenylacetylene base silane resin and preparation method thereof |
| CN103030960A (en) * | 2013-01-06 | 2013-04-10 | 冷晓东 | Production method for lamp housings of environment-friendly glass fiber reinforced plastic composite material street lamps |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1533878A (en) * | 2003-03-27 | 2004-10-06 | 郑光洙 | Resin ceiling and its manufacturing method |
| CN101864076A (en) * | 2010-05-14 | 2010-10-20 | 华东理工大学 | Cyanate resin modified by phenylacetylene base silane resin and preparation method thereof |
| CN103030960A (en) * | 2013-01-06 | 2013-04-10 | 冷晓东 | Production method for lamp housings of environment-friendly glass fiber reinforced plastic composite material street lamps |
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