CN103435988A - 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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- CN103435988A CN103435988A CN2013104128813A CN201310412881A CN103435988A CN 103435988 A CN103435988 A CN 103435988A CN 2013104128813 A CN2013104128813 A CN 2013104128813A CN 201310412881 A CN201310412881 A CN 201310412881A CN 103435988 A CN103435988 A CN 103435988A
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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, relate in particular to phenylacetylene base silane modified unsaturated polyester resin and preparation method thereof.
Background technology
Unsaturated polyester (UP) is the simple linear polymer generated through polycondensation with unsaturated dibasic acid (or acid anhydrides) and dibasic alcohol by saturated, contain non-aromatic unsaturated link(age) in its molecular structure, can cause crosslinking reaction by suitable initiator and form a kind of thermosetting material.The relative density of unsaturated polyester resin is in 1.11～1.20 left and right, and while solidifying, volumetric shrinkage is larger.Processing performance is good is the advantage of unsaturated polyester resin maximum, can at room temperature solidify, and the normal pressure compacted under, processing performance is flexible, is particularly suitable for large-scale and making in site glass fiber reinforced plastics product; Resin good combination property after solidifying, mechanical performance index is a little less than epoxy resin, but is better than resol.Erosion resistance, electrical property and flame retardant resistance can meet the demands by the resin of selecting the suitable trade mark, 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, owing to thering is higher mechanical property, good resistance to chemical attack, weathering resistance and lower cost, be widely used in the industries such as automobile, building, electric and daily necessities.Yet the unsaturated polyester resin resistance toheat is poor, heat-drawn wire is 50～60 ℃, therefore need to carry out modification to it, to meet the application of unsaturated polyester resin in high temperature resistant field.
Improve at present the unsaturated polyester resin thermotolerance both at home and abroad following methods generally arranged:
(1) adopt the high-performance matrix resin to the unsaturated polyester resin modification
Such as using epoxy resin, silicone resin, bimaleimide resin, cyanate ester resin and polyimide resin etc. to carry out modification.For example 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 successively toughened resin, epoxy resin, promotor and mill base to stir, then place deaeration, vacuumize, after exhausting vacuum, add wherein solidifying agent, continue to stir and vacuumize, obtain modified unsaturated polyester resin.
(2) add the second-phase material in unsaturated polyester resin
Add rigid particles and also can improve the thermotolerance of unsaturated polyester resin as nanometer silicon dioxide particle in 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 the system acid number is 10-50mgKOH/g, reaction finishes, and lowers the temperature and adds stopper, paraffin, linking agent; Described reacting nano SiO
2the nano silicon that belongs to in-situ surface finishing, the different times by it in polyreaction adds.
And phenylacetylene base silane is as a kind of novel silicone resin, be characterized in that molecule contains Si-C key and C ≡ C key, can carry out crosslinking curing by the reaction of intramolecule active group, this class 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 field such as aerospace.These polymkeric substance are all usingd 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, comprises aryl, alkyl, hydrogen atom etc., and they have the resistance toheat more much higher than common superpolymer, just day by day cause scientific research personnel's concern.
Summary of the invention
One of purpose of the present invention is to provide employing phenylacetylene base silane modified unsaturated polyester resin, prepare novel organic-inorganic hybrid resin system, to meet various advanced composite material moulding processs, thereby further widen unsaturated polyester resin in the high temperature resistant application that waits high-technology field.Cross-linking and curing reaction occurs and forms tridimensional network in described hybrid systems under the effect of light, heat or chemical initiator, to reach the effect that improves the unsaturated polyester resin resistance toheat.
For reaching this purpose, the present invention adopts following technical scheme:
A kind of high temperature resistant unsaturated polyester resin system, its raw material weight umber comprises: 100 parts of unsaturated polyester resins, 1～100 part of phenylacetylene base silane resin, such as being 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 umber comprises: 100 parts of unsaturated polyester resins, 10～100 parts of phenylacetylene base silane resins.
As optimal technical scheme, high temperature resistant unsaturated polyester resin system of the present invention, its raw material weight umber comprises: 100 parts of unsaturated polyester resins, 30～70 parts of phenylacetylene base silane resins.
The phenylacetylene base silane resin has good solubility in ordinary organic solvents, by the effective viscosity of the hierarchy of control of prepolymerization reaction, is applicable to the moulding process of various advanced composite materials.Ethynyl in the phenylacetylene base silane resin structure has higher reactive behavior, not only moulding at ambient temperature, also can under heat or photochemical effect, by addition reaction, complete curing reaction, in whole solidification process, not have volatile byproducts to produce.But what at first this kind of method will solve is the compatibility problem of two-phase, this is the key that determines material property.
The phenylacetylene base silane resin has good heat-resisting and thermal oxidation, adopts TGA to be studied the resistance toheat of phenylacetylene base silane resin, wherein the Td of methyldiphenyl ethynyl silane in nitrogen
5(decomposition temperature of mass loss 5%) is 615 ℃, and the quality retention rate of 800 ℃ is 91.1%.Phenylacetylene base silane resin and unsaturated polyester resin have good consistency, can carry out modification to unsaturated polyester resin by the mode of physical blending, the ethynyl in the phenylacetylene base silane structure and the carbon-carbon double bond in the unsaturated polyester ester structure formation three-dimensional net structure that can separately or react to each other simultaneously, 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 phenylacetylene base silane resin is the one kind or two or more mixture in tolane base silane resin, three phenylacetylene base silane resins or four phenylacetylene base silane resins.
Shown in the structural formula as I of tolane base silane resin.
Wherein: R1, R2 is alkyl, aryl or hydrogen atom.
Shown in the structural formula as I I of three phenylacetylene base silane resins.
Wherein: R is alkyl, aryl or hydrogen atom.
Shown in the structural formula as I II of four phenylacetylene base silane resins.
One of purpose of the present invention also is to provide the preparation method of described high temperature resistant unsaturated polyester resin system, comprise the steps: the phenylacetylene base silane resin dissolves in unsaturated polyester resin, until completely dissolved, obtain described phenylacetylene silane resin modified unsaturated polyester resin system.This method is the 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, and extremely broad application prospect is arranged in the high-end fields such as national defence, Aeronautics and Astronautics.
Embodiment
Further illustrate technical scheme of the present invention below by embodiment.
The present invention utilizes the 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 forms counts 100 parts of unsaturated polyester resins by weight, 1～100 part of phenylacetylene base silane, until completely dissolved, obtain a kind of phenylacetylene silane resin modified unsaturated polyester resin system.The phenylacetylene base silane resin can be tolane base silane resin, three phenylacetylene base silane resins or four phenylacetylene base silane resins.
Embodiment mono-
At first by adjacent benzene type unsaturated polyester resin 100 weight parts, methyldiphenyl ethynyl silane resin 10 weight parts carry out physical blending, until completely dissolved, prepare the silane-modified unsaturated polyester hybrid resin of methyldiphenyl ethynyl, the heat-drawn wire of this resin system is 102 ℃.
Embodiment bis-
At first by metaphenylene unsaturated polyester resin 100 weight parts, methyl three phenylacetylene base silane resin 25 weight parts carry 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 ℃.
Embodiment tri-
At first by Bisphenol a unsaturated polyester resin 100 weight parts, four phenylacetylene base 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 ℃.
Embodiment tetra-
At first by epoxy acrylic resin 100 weight parts, methyldiphenyl ethynyl silane resin 1 weight part carries out physical blending, until completely dissolved, prepare the silane-modified unsaturated polyester hybrid resin of methyldiphenyl ethynyl, the heat-drawn wire of this resin system is 95 ℃.
Embodiment five
At first by chloro unsaturated polyester resin 100 weight parts, four phenylacetylene base 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 ℃.
Embodiment six
At first by bromo unsaturated polyester resin 100 weight parts, methyl three phenylacetylene base silane resin 75 weight parts carry 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 ℃.
Applicant's statement, 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, do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.The person of ordinary skill in the field should understand, any improvement in the present invention, to the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, the selection of concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (5)
1. a high temperature resistant unsaturated polyester resin system, is characterized in that, its raw material weight umber comprises: 100 parts of unsaturated polyester resins, 1～100 part of phenylacetylene base silane resin.
2. high temperature resistant unsaturated polyester resin system according to claim 1, is characterized in that, its raw material weight umber comprises: 100 parts of unsaturated polyester resins, 10～100 parts of phenylacetylene base silane resins.
3. high temperature resistant unsaturated polyester resin system according to claim 1 and 2, is characterized in that, its raw material weight umber comprises: 100 parts of unsaturated polyester resins, 30～70 parts of phenylacetylene base silane resins.
4. according to the described high temperature resistant unsaturated polyester resin system of claim 1-3 any one, it is characterized in that, described phenylacetylene base silane resin is the one kind or two or more mixture in tolane base silane resin, three phenylacetylene base silane resins or four phenylacetylene base silane resins.
5. the preparation method of the described high temperature resistant unsaturated polyester resin system of claim 1-3 any one, comprise the steps: the phenylacetylene base silane resin dissolves in unsaturated polyester resin, until completely dissolved, obtain described phenylacetylene silane resin modified unsaturated polyester resin system.
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| CN201310412881.3A CN103435988B (en) | 2013-09-11 | 2013-09-11 | High-temperature resistant unsaturated polyester resin system and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN118291013A (en) * | 2024-06-05 | 2024-07-05 | 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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2013
- 2013-09-11 CN CN201310412881.3A patent/CN103435988B/en active Active
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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN118291013A (en) * | 2024-06-05 | 2024-07-05 | 上海申茂电磁线有限公司 | Polyester enameled rectangular copper wire and preparation process 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 |
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