CN103087300B - Unsaturated polyester comprising glycerol monocarboxylate, and resin and application thereof - Google Patents
Unsaturated polyester comprising glycerol monocarboxylate, and resin and application thereof Download PDFInfo
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- CN103087300B CN103087300B CN201110339607.9A CN201110339607A CN103087300B CN 103087300 B CN103087300 B CN 103087300B CN 201110339607 A CN201110339607 A CN 201110339607A CN 103087300 B CN103087300 B CN 103087300B
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- unsaturated polyester
- monocarboxylic acid
- glyceryl ester
- acid glyceryl
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Abstract
The invention relates to unsaturated polyester comprising glycerol monocarboxylate. The unsaturated polyester has a structural unit with alternate non-regular arrangements of two monomer molecules of glycerol monocarboxylate and unsaturated dibasic acid. According to the invention, 15-25% of maleic anhydride by mass, 20-25% of phthalic anhydride by mass, and 55-65% of glycerol monocarboxylate are subjected to condensation; and the material is diluted by using styrene, such that the unsaturated polyester comprising glycerol monocarboxylate is prepared. The unsaturated polyester comprising glycerol monocarboxylate can be used as a universal resin for preparing a glass-fiber-reinforced plastic product. The preparation process of the unsaturated polyester provided by the invention has the advantages of simple process, easy operation, and easy control. The unsaturated polyester has high biocompatibility, and is environmentally friendly. With the unsaturated polyester, production cost is reduced by more than 20%, and a produced product has high stability.
Description
Technical field
The present invention relates to a kind of unsaturated polyester resin, relate in particular to a kind of unsaturated polyester containing monocarboxylic acid glyceryl ester, and the resin that contains this unsaturated polyester, preparation method and purposes.
Background technology
Unsaturated polyester resin (Unsaturated Polyester Resin, UPR) is generally the chain macromolecule compound with ester bond and unsaturated double-bond being formed by unsaturated dibasic acid and dibasic alcohol or monounsaturated dicarboxylic acid and unsaturated dibasic alcohol polycondensation.There is copolymerization again in this mixture, the crosslinked cancellated solid-state material in space that forms under the effect of heat, light or initiator.As the most widely used thermosetting resin of one, that the goods of being made up of it have is lightweight, intensity is high, resistance to chemical attack and the advantageous property such as electrical insulating property is good, and forming method is simple, be convenient to manufacture large-scale or baroque plastics (as: glass reinforced plastic).Unsaturated polyester resin has now been widely used in the fields such as vehicular traffic, building, shipbuilding, chemical industry equipment, electronic apparatus, sports equipment and daily equipment, is the maximum matrix resin of consumption in current composite industry.
Because the starting material of producing unsaturated polyester resin are mainly derived from petroleum chemical industry; but petroleum resources are just day by day exhausted; the price of petrochemicals also sharp rises; in addition the urgency to environment protection; cause the production cost of unsaturated polyester resin sharply to increase, thereby seek efficient, cheap and reproducible alternative materials and prepare unsaturated polyester resin and become the emphasis of technical study.
Home and abroad all has about the research report (J.A.P. Sci.2005,97,825～836 that adopt the synthetic unsaturated polyester resin of bio-based materials; Poly.Eng and Sci., 2007,47,1469～1479; Thermosetting resin, 2008,23,9～12), but these methods of preparing unsaturated polyester resin have all been introduced active group on vegetable fatty acids chain.Due to the complicacy of fatty acid chain structure, the synthesis technique of this class unsaturated polyester resin not only high to equipment requirements, process is loaded down with trivial details, and required production cost is also high, is difficult to realize suitability for industrialized production, and then has limited the use of bio-based materials.So seek novel, efficient and green material, the industrial development of accelerating unsaturated polyester resin is had to extremely important realistic meaning.
Summary of the invention
One object of the present invention is to provide a kind of unsaturated polyester containing monocarboxylic acid glyceryl ester, has two kinds of monomer molecules of monocarboxylic acid glyceryl ester and unsaturated dicarboxylic acid anhydride and replace the structural unit of random arrangement, can replace universal resin.
Another object of the present invention is to provide a kind of unsaturated polyester resin containing monocarboxylic acid glyceryl ester, is formed, to solve depending on unduly petrochemicals by monocarboxylic acid glyceryl ester and unsaturated dicarboxylic acid anhydride polycondensation.
Another object of the present invention is to provide a kind of unsaturated polyester resin containing monocarboxylic acid glyceryl ester, can be used as universal resin for the preparation of glass fiber reinforced plastics product, to solve depending on unduly petrochemicals.
A further object of the present invention is to provide a kind of preparation method of the unsaturated polyester resin containing monocarboxylic acid glyceryl ester, to solve the problem that synthesis process is loaded down with trivial details, equipment requirements is high and production cost is high.
A kind of unsaturated polyester containing monocarboxylic acid glyceryl ester provided by the invention, replaces random being polymerized by monocarboxylic acid glyceride type monomer and anhydrides monomer.
Anhydrides monomer, as: but be not limited only to MALEIC ANHYDRIDE and Tetra hydro Phthalic anhydride.These acid anhydrides can participate in polyreaction as anhydrides monomer simultaneously or separately.
Monocarboxylic acid glyceride type monomer is suc as formula the compound shown in I and formula II.These compounds can participate in polyreaction as monocarboxylic acid glyceride type monomer simultaneously or separately.
In formula, substituent R
1and R
2independently selected from the straight chain in C1～C10, side chain, cycloalkyl or phenyl, preferential straight chain, branched-chain alkyl, cycloalkyl or the phenyl of selecting C1～C6, as: but be not limited only to, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, cyclobutyl, n-pentyl, isopentyl, neo-pentyl and cyclopentyl etc., more preferably select straight chain, branched-chain alkyl or the phenyl of C1～C3, as: methyl, ethyl, n-propyl and sec.-propyl.
The present invention is 1,000Da～3 containing the viscosity-average molecular weight Mv of the unsaturated polyester of monocarboxylic acid glyceryl ester, 000Da, and the molecular weight dispersion coefficient of polyester is 1.5～2.0, and dispersion coefficient is less, and molecular weight of polyesters composition is more even.When molecular weight of polyesters exceedes this scope, along with the increase of molecular weight of polyesters, reaction to terminal afterwards dilution obtain resin solid content and cannot reach service requirements.
Another kind provided by the invention is containing the unsaturated polyester of monocarboxylic acid glyceryl ester, synthetic through polycondensation by MALEIC ANHYDRIDE, Tetra hydro Phthalic anhydride and monocarboxylic acid glyceryl ester.
The contained compound of monocarboxylic acid glyceryl ester of the present invention is suc as formula shown in I and formula II.In formula, substituent R
1and R
2independently selected from the straight chain in C1～C10, side chain, cycloalkyl or phenyl, preferential straight chain, branched-chain alkyl, cycloalkyl or the phenyl of selecting C1～C6, as: but be not limited only to, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, cyclobutyl, n-pentyl, isopentyl, neo-pentyl and cyclopentyl etc., more preferably select straight chain, branched-chain alkyl or the phenyl of C1～C3, as: methyl, ethyl, n-propyl and sec.-propyl.Monocarboxylic acid glyceryl ester or be the compound shown in formula I or formula II, or composition for being formed in any proportion by compound shown in formula I and formula II.
The molecular fraction of MALEIC ANHYDRIDE is 20～35%.The molecular fraction of Tetra hydro Phthalic anhydride is 20～35%.The molecular fraction summation of formula I and formula II is 50～60%.
Another kind provided by the invention, containing the unsaturated polyester of monocarboxylic acid glyceryl ester, is that 15%～25% MALEIC ANHYDRIDE, 20%～25% Tetra hydro Phthalic anhydride and 55%～65% monocarboxylic acid glyceryl ester polycondensation obtain by massfraction.Gained polyester has one or more shown in some formula I and replaces random structural unit, and its viscosity-average molecular weight Mv is 1,000Da～3,000Da, and the molecular weight dispersion coefficient of polyester is 1.5～2.0.
The polycondensation technology of polymkeric substance belongs to the general operation technical ability that those of ordinary skill in the art should possess, also can be according to " coating process (third edition) " (coating process editorial committee volume, Chemical Industry Press, 1997) guidance of a book prepares.As abundant disclosed needs; the present invention enumerates a kind of polycondensation method of the unsaturated polyester containing monocarboxylic acid glyceryl ester; be specially: at 200 DEG C～210 DEG C; through nitrogen protection; be that 15%～25% MALEIC ANHYDRIDE, 20%～25% Tetra hydro Phthalic anhydride and 55%～65% monocarboxylic acid glyceryl ester carry out polycondensation by massfraction; the cone-plate viscosity recording through 150 DEG C of No. 3 rotors is 400Pa.s～450Pa.s, and solid acid number termination reaction while being 36～40mgKOH/g.
The another kind that the present invention enumerates is containing the preparation method of the unsaturated polyester of monocarboxylic acid glyceryl ester, and step is as follows: dropping into massfraction to reaction vessel is successively 15%～25% MALEIC ANHYDRIDE, 20%～25% Tetra hydro Phthalic anhydride and 55%～65% monocarboxylic acid glyceryl ester; Then temperature of reaction is risen to 180 DEG C; In the time heating up in a steamer head beginning water outlet, control stirring velocity at 230r/min～375r/min, control and heat up in a steamer a temperature at 100 DEG C～103 DEG C, temperature of reaction is risen to 200 DEG C～210 DEG C simultaneously; Through 150 DEG C, the cone-plate viscosity that No. 3 rotors record is 400Pa.s～450Pa.s, and solid acid number termination reaction while being 36～40mgKOH/g.
Those of ordinary skill in the art can be according to the guidance of textbook with reference to cited technical scheme, adopts miscellaneous equipment and processing condition to make the unsaturated polyester resin containing monocarboxylic acid glyceryl ester of the present invention.The cited method of the present invention must not be considered as limitation of the present invention.
The present invention who makes to the present invention is 60.0%～66.0% the unsaturated polyester resin containing monocarboxylic acid glyceryl ester containing adding individually or simultaneously vinylbenzene and quinhydrones in the unsaturated polyester of monocarboxylic acid glyceryl ester, being diluted to solid content.As: a kind of unsaturated polyester resin containing monocarboxylic acid glyceryl ester is that 15%～25% MALEIC ANHYDRIDE, 20%～25% Tetra hydro Phthalic anhydride and 55%～65% monocarboxylic acid glyceryl ester polycondensation obtain by massfraction, then forms through vinylbenzene dilution.The present invention regulates making the every chemical property index of resin by the vinylbenzene that adds and the amount of quinhydrones, to meet various actual demands.
Term involved in the present invention is identical with its universal.
Described " C1～C10 ", " C1～C6 " and " C1～C3 " refer to the carbon atom number that group is contained.Because carbon atom cannot exist with the form of mark, for this reason, be appreciated that a kind of simple expression-form, as: in the time that carbonatoms is 1,2,3,4 or 5, be expressed as " carbonatoms C1～C5 " or " C1～C5 ".
Described " solid content " refers to the weight percentage of contained resin solid in resin.
The beneficial effect that technical solution of the present invention realizes:
Unsaturated polyester resin containing monocarboxylic acid glyceryl ester provided by the invention, adopts monocarboxylic acid glyceryl ester and MALEIC ANHYDRIDE and Tetra hydro Phthalic anhydride polycondensation to form, the good stability of product.Preparation technology not only process is simple, is easy to operate and control, and also has very high biocompatibility, environmentally friendly, more makes production cost reduce more than 20%.
The unsaturated polyester resin that the present invention adopts monocarboxylic acid glyceryl ester to produce can be used as resins for universal use and prepares various glass fiber reinforced plastics products, and its Application Areas is extensive.
Embodiment
Below describe technical scheme of the present invention in detail.The embodiment of the present invention is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the art is to be understood that, can modify or be equal to replacement the technical scheme of invention, and not departing from the spirit and scope of technical solution of the present invention, it all should be encompassed in claim scope of the present invention.
If the present invention's reagent used does not clearly indicate, all purchased from Sigma～aldrich (Sigma～Aldrich).
The present invention that each embodiment provides below, containing the unsaturated polyester resin of monocarboxylic acid glyceryl ester, all makes as follows:
Take each component by the listed numerical value of each Example formulations table (being weight), and drop into successively in four-hole boiling flask, Heating temperature is set to 80 DEG C, then temperature of reaction is risen to 180 DEG C; In the time heating up in a steamer head beginning water outlet, control stirring velocity to 230r/min～375r/min, keep heating up in a steamer 100 DEG C～103 DEG C of temperature, temperature of reaction is increased to 200 DEG C～210 DEG C simultaneously; Through 150 DEG C, the cone-plate viscosity that No. 3 rotors record is 400Pa.s～450Pa.s, and termination reaction when solid acid number is 36～40mgKOH/g, cooling immediately, accurately weigh vinylbenzene and quinhydrones by the listed numerical value of formula table (being weight), in the time that temperature is down to 180 DEG C, add quinhydrones, in the time that temperature is down to 160 DEG C～170 DEG C, polyester is poured in thinning tank and stirred, treat that resin dissolves completely and the chemical property index of resin is regulated.The method of each embodiment unsaturated polyester resin performance test institute foundation refers to table 1.
Table 1
Embodiment 1: containing single triacetin unsaturated polyester resin
Table 2
Table 3
The various the present invention that prepare by table 1 in embodiment 1 are carried out to properties test containing single triacetin unsaturated polyester resin, the results are shown in Table 2.Associative list 1 and table 2 are visible, and the unsaturated polyester resins for general purpose making according to the formula of comparative example 1 is better with the wetting property of glass fibre, but the properties such as goods flexural strength, tensile strength do not reach design objective, are not suitable for preparing universal resin.The unsaturated polyester resin intensity making according to the formula of comparative example 2 is higher, but also better with glass fibre wetting property, therefore be applicable to the universal resin of preparation.According to formula 1～formula 4 unsaturated polyester resins of producing of filling a prescription, the physical strength of goods is high, also good with the wetting property of glass, can meet the requirement of the application in various situations.
Embodiment 2: containing single butanic acid glyceryl ester unsaturated polyester resin
Table 4
Table 5
The various the present invention that prepare by table 4 in embodiment 2 are carried out to properties test containing single butanic acid glyceryl ester unsaturated polyester resin, the results are shown in Table 5.Associative list 4 and table 5 are visible, the unsaturated polyester resins for general purpose making according to the formula of comparative example 1, though better with the wetting property of glass fibre, the properties such as goods flexural strength, tensile strength do not reach design objective, therefore be not suitable for preparing universal resin.Though the unsaturated polyester resin intensity making according to the formula of comparative example 2 is higher, poor with glass fibre wetting property, therefore be also not suitable for preparing universal resin.According to formula 1～formula 4 unsaturated polyester resins of producing of filling a prescription, the physical strength of goods is high, also good with the wetting property of glass, can meet the requirement of the application in various situations.
Embodiment 3: containing single phenylformic acid glyceryl ester unsaturated polyester resin
Table 6
Table 7
The various the present invention that prepare by table 6 in embodiment 3 are carried out to properties test containing single phenylformic acid glyceryl ester unsaturated polyester resin, the results are shown in Table 7.Associative list 6 and table 7 are visible, the unsaturated polyester resins for general purpose making according to the formula of comparative example 1, though better with the wetting property of glass fibre, the properties such as goods flexural strength, tensile strength do not reach design objective, therefore be not suitable for preparing universal resin.Though the unsaturated polyester resin intensity making according to the formula of comparative example 2 is higher, poor with glass fibre wetting property, therefore be also not suitable for preparing universal resin.According to formula 1～formula 4 unsaturated polyester resins of producing of filling a prescription, the physical strength of goods is high, also good with the wetting property of glass, can meet the requirement of the application in various situations.
Claims (7)
1. containing a unsaturated polyester for monocarboxylic acid glyceryl ester, it is characterized in that by massfraction being that 15%～25% MALEIC ANHYDRIDE, 20%～25% Tetra hydro Phthalic anhydride and 55%～65% monocarboxylic acid glyceryl ester polycondensation obtain; Described monocarboxylic acid glyceryl ester contains individually or simultaneously suc as formula the compound shown in I and formula II:
In formula, substituent R
1and R
2independently selected from the straight chain in C1～C10, side chain, cycloalkyl or phenyl.
2. the unsaturated polyester containing monocarboxylic acid glyceryl ester according to claim 1, is characterized in that the molecular weight dispersion coefficient of described polyester is 1.5～2.0.
3. the unsaturated polyester containing monocarboxylic acid glyceryl ester according to claim 1, is characterized in that described substituent R
1and R
2independently selected from methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, cyclobutyl, n-pentyl, isopentyl, neo-pentyl, cyclopentyl or phenyl.
4. the unsaturated polyester containing monocarboxylic acid glyceryl ester according to claim 1; the preparation method who it is characterized in that described polyester is as follows: at 200 DEG C～210 DEG C; through nitrogen protection; be that 15%～25% MALEIC ANHYDRIDE, 20%～25% Tetra hydro Phthalic anhydride and 55%～65% monocarboxylic acid glyceryl ester carry out polycondensation by massfraction; through 150 DEG C; the cone-plate viscosity that No. 3 rotors record is 400Pa.s～450Pa.s, and solid acid number termination reaction while being 36～40mgKOH/g.
5. the unsaturated polyester containing monocarboxylic acid glyceryl ester according to claim 1, is characterized in that the preparation method of described polyester is as follows: dropping into massfraction to reaction vessel is successively 15%～25% MALEIC ANHYDRIDE, 20%～25% Tetra hydro Phthalic anhydride and 55%～65% monocarboxylic acid glyceryl ester; Then temperature of reaction is risen to 180 DEG C; In the time heating up in a steamer head beginning water outlet, control stirring velocity is 230r/min～375r/min, controls and heats up in a steamer a temperature at 100 DEG C～103 DEG C, temperature of reaction is risen to 200 DEG C～210 DEG C simultaneously; Through 150 DEG C, the cone-plate viscosity that No. 3 rotors record is 400Pa.s～450Pa.s, and solid acid number termination reaction while being 36～40mgKOH/g.
6. containing a unsaturated polyester resin for monocarboxylic acid glyceryl ester, it is characterized in that adding individually or simultaneously vinylbenzene and quinhydrones dilute and obtain to the unsaturated polyester containing monocarboxylic acid glyceryl ester claimed in claim 1, solid content is 60.0%～66.0%.
7. the unsaturated polyester resin containing monocarboxylic acid glyceryl ester according to claim 6, it is characterized in that described unsaturated polyester resin as resins for universal use for the preparation of glass fiber reinforced plastics product.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110339607.9A CN103087300B (en) | 2011-10-31 | 2011-10-31 | Unsaturated polyester comprising glycerol monocarboxylate, and resin and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110339607.9A CN103087300B (en) | 2011-10-31 | 2011-10-31 | Unsaturated polyester comprising glycerol monocarboxylate, and resin and application thereof |
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| CN103087300A CN103087300A (en) | 2013-05-08 |
| CN103087300B true CN103087300B (en) | 2014-07-23 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101608015A (en) * | 2009-07-20 | 2009-12-23 | 常州市华润复合材料有限公司 | A kind of unsaturated polyester resin and method for making thereof that is used for electrical apparatus product moulding material |
| CN102115534A (en) * | 2011-01-07 | 2011-07-06 | 中国林业科学研究院林产化学工业研究所 | Dicyclopentadiene type unsaturated polyester modified by tung oil, and preparation method and application thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101608015A (en) * | 2009-07-20 | 2009-12-23 | 常州市华润复合材料有限公司 | A kind of unsaturated polyester resin and method for making thereof that is used for electrical apparatus product moulding material |
| CN102115534A (en) * | 2011-01-07 | 2011-07-06 | 中国林业科学研究院林产化学工业研究所 | Dicyclopentadiene type unsaturated polyester modified by tung oil, and preparation method and application thereof |
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Address after: 213101 Jiangsu Province, Changzhou city Wujin District Henglin town Cui New Cross Road No. 92 Patentee after: Changzhou Huarun Composite Materials Co., Ltd. Patentee after: Jiangsu Baihe Paint Co., Ltd. Address before: 213101, 7 floor, building 5, Times Square, 396 Tongjiang Avenue, Xinbei District, Jiangsu, Changzhou Patentee before: Changzhou Huarun Composite Materials Co., Ltd. Patentee before: Jiangsu Baihe Paint Co., Ltd. |
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