CN101555308B - Unsaturated polyester resin for alpine rock - Google Patents
Unsaturated polyester resin for alpine rock Download PDFInfo
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- CN101555308B CN101555308B CN2008101951329A CN200810195132A CN101555308B CN 101555308 B CN101555308 B CN 101555308B CN 2008101951329 A CN2008101951329 A CN 2008101951329A CN 200810195132 A CN200810195132 A CN 200810195132A CN 101555308 B CN101555308 B CN 101555308B
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Abstract
The invention discloses an unsaturated polyester resin for alpine rock, comprising the following components by part by weight: 54-59 parts of unsaturated polyester, 28-33 parts of cross-linking agents, 7-13 parts of retarders and 2-5 parts of nanometer-sized composite polyester resin. The retarder is vinyltoluene or 3-phenylpropylene. The cross-linking agent is styrene or methyl methacrylate. The unsaturated polyester resin of the invention avoids the phenomenon that stones crack due to too concentrated heat discharged from the resin in the process of shaping large stones. The resin has the coating effect. The artificial marble processed by the unsaturated polyester resin of the invention has low water absorption and no radioactivity, and has performances excelling that of natural marbles.
Description
Technical field
The present invention relates to a kind of unsaturated polyester resin, especially relate to a kind of unsaturated polyester resin for alpine rock.
Background technology
The technological process of producing at present artificial marble is: marble is mixed joining die for molding after the stirring and obtain 5～6m with unsaturated polyester resin with filler
3Large-scale hilllock stone, size is on request cut, polishes, is polished and obtain satisfactory artificial marble then.
Because existing unsaturated polyester resin can be emitted a large amount of heats at short notice when solidifying, and for large-scale hilllock stone, liberated heat is not easy to external diffusion, can cause stone material cracking like this, has not only reduced the volume ratio of stone material but also can influence the quality of stone material.Generally for fear of stone material cracking, can improve the ratio of saturated acid and unsaturated acid in the resin formula, still can make the physical strength of stone material not reach requirement like this, the marble surface gloss after the processing is very poor.
Summary of the invention
The objective of the invention is to overcome the problems referred to above, provide a kind of hilllock stone of can avoiding when moulding, to ftracture, can make hilllock stone have the unsaturated polyester resin for alpine rock of higher brightness and luster effect through the marble that obtains after processing again.
The technical scheme that realizes the object of the invention is: a kind of unsaturated polyester resin for alpine rock comprises following components by part by weight: 2～5 parts of 54～59 parts of unsaturated polyesters, 28～33 parts of linking agents, 7～13 parts of retarders and nano composite polyester resins.
Described nano composite polyester resin is the compound hydroxyl telechelic polyester resin of nano silicon, its preparation method is: in the 500ml four-hole boiling flask that thermometer, condenser, nitrogen mouth, agitator are housed, add 1.0mol 11 carbon dicarboxylic acids, 1.3mol 1, the polyoxyethylene glycol of 4-butyleneglycol, 0.7mol molecular weight 200, nanometer titanium dioxide silicone content account for the silicon dioxide gel of total resin weight 14%, be warming up to the solvent that 120 ℃ of heating were removed in the colloidal sol in 30 minutes, continue to be warming up to 160-180 ℃, reacted 4 hours, slowly be chilled to room temperature, discharging promptly.
3～5 parts of 56～58 parts of preferred unsaturated polyesters, 30～32 parts of linking agents, 8～10 parts of retarders and nano composite polyester resins.
More preferably 57 parts of unsaturated polyesters, 31 parts of linking agents, 9 parts of retarders and nano composite polyester resin are 3 parts.
Wherein unsaturated polyester is mixed and made into by propylene glycol, ethylene glycol, glycol ether, phthalic anhydride, suitable bar.Wherein the mol ratio of phthalic anhydride and cis-butenedioic anhydride is 4: 5, and resin has certain mechanical strength after curing like this.
Linking agent is vinylbenzene or methyl methacrylate, optimization styrene.
Retarder is the compound that a class has unsaturated double-bond, comprises vinyl toluene or 3-phenyl propylene.They can dissolve each other with crosslinking styrene or methyl methacrylate, also can be compatible with unsaturated polyester, under the effect of solidifying agent can also with resin solidification, liberated heat is constant, but exothermic speed is obviously slack-off, exothermic peak temperature is descended, therefore the cracking situation of hilllock stone when moulding reduced greatly.The retarder addition is more little, and hilllock stone rimose situation is just big more, but addition is excessive, and the surface quality after the processing of stone will descend.
Nano composite polyester resin is the nano composite polyester resin of the disclosed high-solid lower-viscosity of Chinese patent CN1268685C.It joins in the unsaturated polyester resin when solidifying, can reduce the shrinking percentage, particularly resin solidification of resin like this after, after the processing of stone material economy-combat grinding and polishing light, the gloss of stone surface and brightness are improved greatly, have coating result.Nano level vibrin addition is very few, and the coating result of the stone surface after the processing is just not obvious, and addition is excessive, and the cost of unsaturated polyester resin will strengthen, and the mechanical property of stone material also can descend on the contrary.
The production method of unsaturated polyester resin for alpine rock of the present invention is: prepare unsaturated polyester earlier, then with its dilution, in the thinner except crosslinking styrene, also add retarder, after fully stirring, add nano composite polyester resin again, can obtain unsaturated polyester resin through abundant stirring.
The present invention has positive effect: (1) the present invention prolongs the exothermic process of resin when solidifying by adding retarder, just reduce the exothermic peak of resin, can avoid large-stone when moulding, too concentrate the appearance that causes stone material cracking situation because of the resin liberated heat.(2) the present invention makes stone material through having the effect of similar coatings after particularly polishing after processing by adding nano composite polyester resin.(3) low with unsaturated polyester resin artificial marble processed water-intake rate of the present invention, there is not radioactivity, performance is better than natural marble.
Embodiment
(embodiment 1)
The unsaturated polyester resin for alpine rock of present embodiment comprises following components by part by weight: 3 parts of 57 parts of unsaturated polyesters, vinylbenzene 31,9 parts of vinyl toluenes and nano composite polyester resins.
Its preparation method is: the unsaturated polyester that the cis-butenedioic anhydride (1.0mol) of the phthalic anhydride (0.8mol) of the glycol ether (0.4mol) of the ethylene glycol (0.5mol) of the propylene glycol (1.0mol) of 76g, 32g, 42g, 118g and 98g is mixed and made into 330g.Get this unsaturated polyester of 57g and add the thinner that contains 31g vinylbenzene and 9g vinyl toluene and dilute, after fully stirring, add the nano composite polyester resin that 3g makes according to the embodiment 1 of Chinese patent CN1268685C again, promptly get unsaturated polyester resin through fully stirring again.
The described nano composite polyester resin that makes according to the embodiment 1 of Chinese patent CN1268685C is the compound hydroxyl telechelic polyester resin of nano silicon, its preparation method is: thermometer is being housed, condenser, the nitrogen mouth, in the 500ml four-hole boiling flask of agitator, add 1.0mol 11 carbon dicarboxylic acids, 1.3mol 1, the 4-butyleneglycol, 0.7mol the polyoxyethylene glycol of molecular weight 200, the nanometer titanium dioxide silicone content accounts for the silicon dioxide gel of total resin weight 14%, be warming up to the solvent that 120 ℃ of heating were removed in the colloidal sol in 30 minutes, continue to be warming up to 160-180 ℃, reacted 4 hours, slowly be chilled to room temperature, discharging promptly.
Measure the exothermic peak temperature of this unsaturated polyester resin when solidifying earlier, make casting matrix then, survey its physical data, concrete outcome sees Table 1.Marmorean glossiness with this unsaturated polyester resin machine-shaping can reach 96%.
(embodiment 2～embodiment 6)
Each embodiment is substantially the same manner as Example 1, and difference sees Table 1.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| Unsaturated polyester | ?57g | ?57g | ?55g | 56g | 57g | ?58g |
| Linking agent | Vinylbenzene 31g | Vinylbenzene 30g | Vinylbenzene 32g | Methyl methacrylate 32g | Vinylbenzene 28g | Methyl methacrylate 31g |
| Retarder | Vinyl toluene 9g | Vinyl toluene 10g | Vinyl toluene 8g | 3-phenyl propylene 9g | 3-phenyl propylene 13g | Vinyl toluene 7g |
| Nano composite polyester resin | ?3g | ?3g | ?5g | 3g | 2g | ?4g |
| Exothermic peak temperature (℃) | ?84 | ?78 | ?96 | 88 | 98 | ?95 |
| Ba Keer hardness | ?46 | ?44 | ?46 | 47 | 48 | ?47 |
| Tensile strength (MPa) | ?63 | ?58.1 | ?59 | 60 | 64 | ?62 |
| Flexural strength (MPa) | ?89 | ?96 | ?89 | 88 | 92 | ?91 |
| Water-intake rate (%) | ?0.16 | ?0.15 | ?0.16 | 0.15 | 0.17 | ?0.16 |
| Goods glossiness (%) | ?96 | ?97 | ?95 | 92 | 97 | ?96 |
(Comparative Examples 1～Comparative Examples 6)
Each Comparative Examples is substantially the same manner as Example 1, and difference sees Table 2.
Table 2
| Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 | Comparative Examples 4 | Comparative Examples 5 | Comparative Examples 6 | |
| Unsaturated polyester | ?57g | ?53g | ?55g | 57g | ?57g | ?62g |
| Linking agent | Vinylbenzene 33g | Vinylbenzene 26g | Vinylbenzene 37g | Vinylbenzene 31g | Vinylbenzene 38g | Vinylbenzene 38g |
| Retarder | Vinyl toluene 9g | Vinyl toluene 14g | Vinyl toluene 3g | 3-phenyl propylene 12g | ?- | ?- |
| Nano composite polyester resin | ?1g | ?7g | ?5g | - | ?5g | ?- |
| Exothermic peak temperature (℃) | ?84 | ?67 | ?116 | 98 | ?155 | ?165 |
| Ba Keer hardness | ?46 | ?44 | ?48 | 46 | ?50 | ?52 |
| Tensile strength (MPa) | ?63 | ?58 | ?76 | 70 | ?65 | ?71 |
| Flexural strength (MPa) | 89 | 98 | 93 | 87 | 92 | 87 |
| Water-intake rate (%) | 0.16 | 0.18 | 0.15 | 0.15 | 0.16 | 0.15 |
| Goods glossiness (%) | 88 | 96 | 98 | 72 | 96 | 74 |
Annotate: in table 1 and the table 2, exothermic peak temperature (℃) term of reference be 70～90, the term of reference of Ba Keer hardness is 〉=40, the term of reference of tensile strength (MPa) is 〉=55, the term of reference of flexural strength (MPa) is 〉=80, the term of reference of water-intake rate (%) is≤0.2, goods glossiness (%) 〉=95.
As can be seen from Table 1: the unsaturated polyester resin of each embodiment preparation, exothermic peak temperature is moderate, substantially can avoid the rimose situation to occur in the stone production process on duty, the mechanical property of resin can be guaranteed again, satisfies the requirement of producing large artificial marble hilllock stone.
As can be seen from Table 2:
The Comparative Examples 3 that retarder is less and do not add the Comparative Examples 5 of retarder and the unsaturated polyester resin that Comparative Examples 6 is made, exothermic peak temperature when it solidifies is too high, therefore when the stone of production hilllock, when especially producing large-scale hilllock stone, heat release is too concentrated, the volume that adds stone on duty is very big, and heat radiation is difficulty relatively, so hilllock stone rimose possibility will be strengthened.
The Comparative Examples 1 that nano composite polyester resin is less and do not add the Comparative Examples 4 of nanometer composite polyester resin and the unsaturated polyester resin that Comparative Examples 6 is made, the marmorean glossiness after the machine-shaping is lower.
The unsaturated polyester resin that the more Comparative Examples 2 of retarder and nano composite polyester resin is made, its exothermic peak temperature is low excessively, though stone not conference of rimose situation when moulding in hilllock occurs, but its mechanical property is very undesirable, especially Ba Ke hardness is lower, water-intake rate rises, and is not suitable for as hilllock stone resin.
Claims (7)
1. unsaturated polyester resin for alpine rock is characterized in that: comprise following components by part by weight: 2～5 parts of 54～59 parts of unsaturated polyesters, 28～33 parts of linking agents, 7～13 parts of retarders and nano composite polyester resins,
Described nano composite polyester resin is the compound hydroxyl telechelic polyester resin of nano silicon, its preparation method is: in the 500ml four-hole boiling flask that thermometer, condenser, nitrogen mouth, agitator are housed, add 1.0mol 11 carbon dicarboxylic acids, 1.3mol 1, the polyoxyethylene glycol of 4-butyleneglycol, 0.7mol molecular weight 200, nanometer titanium dioxide silicone content account for the silicon dioxide gel of total resin weight 14%, be warming up to the solvent that 120 ℃ of heating were removed in the colloidal sol in 30 minutes, continue to be warming up to 160-180 ℃, reacted 4 hours, slowly be chilled to room temperature, discharging promptly.
2. unsaturated polyester resin for alpine rock according to claim 1 is characterized in that: comprise following components by part by weight: 3～5 parts of 56～58 parts of unsaturated polyesters, 30～32 parts of linking agents, 8～10 parts of retarders and nano composite polyester resins.
3. unsaturated polyester resin for alpine rock according to claim 2 is characterized in that: comprise following components by part by weight: 3 parts of 57 parts of unsaturated polyesters, 31 parts of linking agents, 9 parts of retarders and nano composite polyester resins.
4. according to the described unsaturated polyester resin for alpine rock of one of claim 1 to 3, it is characterized in that: described retarder is vinyl toluene or 3-phenyl propylene.
5. according to the described unsaturated polyester resin for alpine rock of one of claim 1 to 3, it is characterized in that: described linking agent is vinylbenzene or methyl methacrylate.
6. according to the described unsaturated polyester resin for alpine rock of one of claim 1 to 3, it is characterized in that: described unsaturated polyester is mixed and made into by dibasic alcohol and dibasic acid anhydride, described dibasic alcohol comprises propylene glycol, ethylene glycol and glycol ether, and described dibasic acid anhydride is phthalic anhydride and cis-butenedioic anhydride.
7. unsaturated polyester resin for alpine rock according to claim 6 is characterized in that: the mol ratio of described phthalic anhydride and cis-butenedioic anhydride is 4: 5.
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| CN2008101951329A CN101555308B (en) | 2008-11-06 | 2008-11-06 | Unsaturated polyester resin for alpine rock |
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| CN2008101951329A CN101555308B (en) | 2008-11-06 | 2008-11-06 | Unsaturated polyester resin for alpine rock |
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| CN101555308A CN101555308A (en) | 2009-10-14 |
| CN101555308B true CN101555308B (en) | 2011-09-28 |
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| CN2008101951329A Expired - Fee Related CN101555308B (en) | 2008-11-06 | 2008-11-06 | Unsaturated polyester resin for alpine rock |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735407B (en) * | 2009-12-17 | 2011-12-21 | 江苏大力士投资有限公司 | Method for preparing manmade stone unsaturated resin |
| PL2338940T3 (en) * | 2009-12-23 | 2017-04-28 | Silicalia S.L. | Composition for coating |
| CN104026812B (en) * | 2014-06-19 | 2016-06-08 | 浙江伟星实业发展股份有限公司 | The preparation method of a kind of unsaturated polyester resin button |
| CN106632880B (en) * | 2016-12-22 | 2018-09-25 | 嘉兴市清河高力绝缘有限公司 | Curing agent and its preparation process for unsaturated polyester insulating lacquer |
| CN108084419B (en) * | 2017-12-30 | 2020-02-07 | 方亨 | Modified unsaturated polyester resin and preparation method thereof |
| CN115626791B (en) * | 2022-11-02 | 2023-06-09 | 陕西安东兴阳岗石科技有限公司 | Nano calcium enhanced additive, resin and artificial granite |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5314729A (en) * | 1990-07-30 | 1994-05-24 | Dainippon Ink And Chemicals, Inc. | Artificial marble |
| CN1164896A (en) * | 1994-09-30 | 1997-11-12 | 阿莫利特图章有限公司 | Polyester resin-based high index ophthalmic lenses having improved optical uniformity and/or tintability |
| CN1635025A (en) * | 2004-12-06 | 2005-07-06 | 复旦大学 | High solidness low viscosity nano composite polyester resin and method of preparation |
| CN1749196A (en) * | 2004-09-17 | 2006-03-22 | 上海懿德克林装饰材料有限公司 | Artificial stone table top and its producing method and use |
-
2008
- 2008-11-06 CN CN2008101951329A patent/CN101555308B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5314729A (en) * | 1990-07-30 | 1994-05-24 | Dainippon Ink And Chemicals, Inc. | Artificial marble |
| CN1164896A (en) * | 1994-09-30 | 1997-11-12 | 阿莫利特图章有限公司 | Polyester resin-based high index ophthalmic lenses having improved optical uniformity and/or tintability |
| CN1749196A (en) * | 2004-09-17 | 2006-03-22 | 上海懿德克林装饰材料有限公司 | Artificial stone table top and its producing method and use |
| CN1635025A (en) * | 2004-12-06 | 2005-07-06 | 复旦大学 | High solidness low viscosity nano composite polyester resin and method of preparation |
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