CN104031250B - The preparation method of unsaturated polyester resin mill base vector resin - Google Patents
The preparation method of unsaturated polyester resin mill base vector resin Download PDFInfo
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- CN104031250B CN104031250B CN201410269127.3A CN201410269127A CN104031250B CN 104031250 B CN104031250 B CN 104031250B CN 201410269127 A CN201410269127 A CN 201410269127A CN 104031250 B CN104031250 B CN 104031250B
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Abstract
The present invention discloses the preparation method of a kind of unsaturated polyester resin mill base vector resin, adds dibasic alcohol 70��95 parts, diprotic acid 60��85 parts, MALEIC ANHYDRIDE 18��20 parts in reactor, leads to and also stir evenly into nitrogen in reactor; Heating up gradually makes reactor temperature be 200��220 DEG C, carries out condensation reaction at such a temperature; After question response system becomes homogeneous transparent, insulation continues reaction until recording reaction product acid number to be less than 20mgKOH/g; Described dibasic alcohol is glycol ether or dipropylene glycol, and described polyprotonic acid is hexanodioic acid or SA; The product being obtained by reacting is cooled to 180 DEG C��190 DEG C, in product, then adds Resorcinol 5��6 parts, stir after evenly and material is cooled to less than 40 DEG C, filter and obtain unsaturated polyester resin mill base vector resin. Obtained unsaturated polyester presents good liquid state, is applicable to mill base and uses, and the stability of pigment paste being mixed with is good.
Description
Technical field
The present invention relates to the preparation method of a kind of resin, it is specifically related to the preparation method of a kind of unsaturated polyester resin mill base vector resin.
Background technology
Unsaturated polyester resin mill base is disperseed by pigment with auxiliary agent process in proprietary carrier and grind, can be painted for unsaturated polyester resin glass fiber reinforced plastics product; In use, by a certain percentage mill base and unsaturated polyester resin Homogeneous phase mixing, just obtaining the goods with required color after shaping, concrete color can be prepared on request.
Mill base only possesses the effect that good tint permanence just can greatly play pigment, thus when same color and colour strength, color paste consumption is minimum, and opacifying power is the strongest. Meanwhile, high performance mill base has complete specification of quality system in quality, has higher weathering resistance, it is possible to be applicable to tinting system and color management software thereof. Unsaturated polyester resin mill base has the features such as lovely luster, heat-resisting, steady quality and strong coloring force.
The main component of unsaturated polyester resin mill base comprises pigment powder, auxiliary agent and vector resin. The requirement of vector resin is the dispersion of depot, pigment and to be got well with unsaturated polyester resin consistency by unsaturated polyester resin mill base, it may also be useful to time, do not affect the processing characteristics of unsaturated polyester resin.
At present, the carrier that unsaturated polyester resin mill base uses is monomer or low reactivity unsaturated polyester mostly. Monomer often has its own shortcomings: one is on the high side; Two is not good, the easy layering of the stability of pigment paste being mixed with; Three is in use, not good with unsaturated polyester resin consistency, affects the intensity of goods simultaneously; Four is have certain smell. Low reactivity unsaturated polyester often has its own shortcomings: one is in use, affects the performance of unsaturated polyester resin, particularly intensity, aging resistance; Two is due to low reactivity, and volatile matter can be many, human body and environment is harmful to; Three is that snappiness is inadequate; Four is the intensity affecting goods to a certain extent.
Chinese patent literature CN101434692B(application number 200810243471.X) disclose the preparation method of a kind of color sizing vector resin, drop in the Tetra hydro Phthalic anhydride of the MALEIC ANHYDRIDE of the ethylene glycol of the glycol ether of weight 110-190 part, 15-30 part and 35-65 part, 55-95 part in reactor, between 160 DEG C��170 DEG C, carry out esterification 2 to 3 hours; Esterification is carried out 2 to 3 hours between 170 DEG C��180 DEG C; Esterification is carried out 2 to 3 hours between 180 DEG C��200 DEG C; The complete mensuration acid number of esterification, is cooled to less than 120 DEG C, filters and packages obtained finished product. But the medium and small molecular ratio of the vector resin produced according to this method is more, so that the volatile matter of vector resin is many, and in addition, when being configured to mill base use with vector resin, small molecules may react with unsaturated polyester resin, reduces the intensity of unsaturated polyester resin.
Summary of the invention
Technical problem to be solved by this invention is to provide the preparation method of a kind of reactive behavior height, molecular weight height, unsaturated polyester resin mill base vector resin that volatile matter is few.
The technical scheme realizing the object of the invention is the preparation method of a kind of unsaturated polyester resin mill base vector resin, comprises the following steps:
1. in reactor, add dibasic alcohol 70��95 parts, polyprotonic acid 60��85 parts, MALEIC ANHYDRIDE 18��20 parts, lead in reactor and also stir evenly into nitrogen; Stir even after heat up gradually and make reactor temperature be 200 DEG C��220 DEG C, at such a temperature and under nitrogen protection, in reactor, carry out condensation reaction; After question response system becomes homogeneous transparent, insulation continues reaction until recording reaction product acid number to be less than 20mgKOH/g; Described dibasic alcohol is glycol ether or dipropylene glycol, and described polyprotonic acid is hexanodioic acid or SA.
2. the product that 1. step is obtained by reacting is cooled to 180 DEG C��190 DEG C, in product, then adds Resorcinol 5��6 parts, stir after evenly and material is cooled to less than 40 DEG C, filter and obtain unsaturated polyester resin mill base vector resin.
Above-mentioned steps 1. in reaction mass rise in temperature per hour 5.0��10.0 DEG C when heating up gradually.
2. above-mentioned steps adds Resorcinol in product and stirs after evenly when being cooled by material, adopts the type of cooling that cold and hot thermal oil exchanges, and temperature of charge per hour declines 10.0 DEG C��30.0 DEG C.
The present invention has positive effect: the high-performance mill base vector resin of (1) the present invention is the unsaturated polyester of a kind of relatively high reaction activity, higher molecular weight; Usual aforesaid unsaturated polyester is solid-state or semi-solid state, but the dibasic alcohol that the present invention selects molecular structure longer on starting material are selected, diprotic acid, unsaturated polyester obtained like this presents good liquid state, is applicable to mill base and uses, and the stability of pigment paste being mixed with is good; Vector resin again can be compatible preferably with unsaturated polyester resin simultaneously, participates in crosslinking reaction, and the intensity not affecting final resin even can improve the intensity of goods, and snappiness might as well; Due to relatively high reaction activity, higher molecular weight, so volatile matter is less, environmental friendliness.
(2) when the present invention prepares vector resin, first at high temperature complete condensation reaction, it is cooled to after below 190 DEG C, in condensation product, adds Resorcinol, be cooled to less than 40 DEG C after mixed even and obtain vector resin; The activity of the vector resin of the present invention is higher, adds Resorcinol as stopper, it is possible to vector resin is preserved for a long time.
Embodiment
(embodiment 1)
The preparation method of the unsaturated polyester resin mill base vector resin of the present embodiment comprises the following steps:
1. in reactor, add dipropylene glycol 930g, hexanodioic acid 600g, MALEIC ANHYDRIDE 185g, lead in reactor and also stir evenly into nitrogen; Stir even after heat up gradually and make reactor temperature be 210 DEG C, at such a temperature and under nitrogen protection, in reactor, carry out condensation reaction; After question response system becomes homogeneous transparent, 210 DEG C are kept to continue reaction until recording reaction product acid number to be less than 20mgKOH/g.
2. the product that 1. step is obtained by reacting is cooled to 180 DEG C��190 DEG C, in product, then adds Resorcinol 60g, stir after evenly and material is cooled to less than 40 DEG C, filter and obtain unsaturated polyester resin mill base vector resin. The type of cooling that cold and hot thermal oil exchanges is adopted during material cooling.
The vector resin that the present embodiment obtains is light yellow clear liquid, and viscosity (25 DEG C, mPa.S) is 4.85, and acid number mgKOH/g is 16.2. Molecular weight is 2000��2500.
The unsaturated polyester of usual aforementioned molecular weight is solid-state or semi-solid state, but the present invention select molecular structure longer on starting material are selected dibasic alcohol, diprotic acid, unsaturated polyester obtained like this presents good liquid state, is applicable to mill base use.
(embodiment 2)
All the other are identical with embodiment 1 for the preparation method of the unsaturated polyester resin mill base vector resin of the present embodiment, and difference is: step 1. in reactor, add dipropylene glycol 930g, SA 830g, MALEIC ANHYDRIDE 185g.
Step 1. in reactor temperature rise to 210 DEG C, at such a temperature and under nitrogen protection, in reactor, carry out condensation reaction.
The vector resin that the present embodiment obtains is light yellow clear liquid, and viscosity (25 DEG C, mPa.S) is 5.10, and acid number mgKOH/g is 15.9. Molecular weight is 2100��2600.
(embodiment 3)
All the other are identical with embodiment 1 for the preparation method of the unsaturated polyester resin mill base vector resin of the present embodiment, and difference is: step 1. in reactor, add glycol ether 735g, hexanodioic acid 600g, MALEIC ANHYDRIDE 185g.
Step 1. in reactor temperature rise to 210 DEG C, at such a temperature and under nitrogen protection, in reactor, carry out condensation reaction.
The vector resin that the present embodiment obtains is light yellow clear liquid, and viscosity (25 DEG C, mPa.S) is 4.60, and acid number mgKOH/g is 16.8. Molecular weight is 1800��2300.
(embodiment 4)
All the other are identical with embodiment 1 for the preparation method of the unsaturated polyester resin mill base vector resin of the present embodiment, and difference is: step 1. in reactor, add glycol ether 735g, SA 830g, MALEIC ANHYDRIDE 185g.
Step 1. in reactor temperature rise to 215 DEG C, at such a temperature and under nitrogen protection, in reactor, carry out condensation reaction.
The vector resin that the present embodiment obtains is light yellow clear liquid, and viscosity (25 DEG C, mPa.S) is 4.80, and acid number mgKOH/g is 16.0. Molecular weight is 2000��2500.
Claims (3)
1. the preparation method of a unsaturated polyester resin mill base vector resin, it is characterised in that comprise the following steps:
1. in reactor, add dibasic alcohol 70��95 parts, diprotic acid 60��85 parts, MALEIC ANHYDRIDE 18��20 parts, lead in reactor and also stir evenly into nitrogen; Stir even after heat up gradually and make reactor temperature be 200 DEG C��220 DEG C, at such a temperature and under nitrogen protection, in reactor, carry out condensation reaction; After question response system becomes homogeneous transparent, insulation continues reaction until recording reaction product acid number to be less than 20mgKOH/g; Described dibasic alcohol is glycol ether or dipropylene glycol, and described diprotic acid is hexanodioic acid or sebacic acid;
2. the product that 1. step is obtained by reacting is cooled to 180 DEG C��190 DEG C, then in product, add Resorcinol 5��6 parts, stir after evenly and material is cooled to less than 40 DEG C, filter and obtain the unsaturated polyester resin mill base vector resin that molecular weight is 2000��2600.
2. the preparation method of unsaturated polyester resin mill base vector resin according to claim 1, it is characterised in that: step 1. in reaction mass rise in temperature per hour 5.0��10.0 DEG C when heating up gradually.
3. the preparation method of unsaturated polyester resin mill base vector resin according to claim 1, it is characterized in that: 2. step adds Resorcinol in product and stir after evenly when being cooled by material, adopting the type of cooling that cold and hot thermal oil exchanges, temperature of charge per hour declines 10.0 DEG C��30.0 DEG C.
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| CN105085885A (en) * | 2015-09-21 | 2015-11-25 | 永悦科技股份有限公司 | Colorant matrix resin for unsaturated polyester resin and preparation method thereof |
| CN110903472A (en) * | 2018-09-15 | 2020-03-24 | 福建省南安市华龙树脂有限公司 | Preparation method of polyester for low-viscosity color paste matrix |
| WO2020066651A1 (en) * | 2018-09-27 | 2020-04-02 | Dic株式会社 | Fluidity modifier, composition containing same, and cured product of said composition |
| CN109575258A (en) * | 2018-11-27 | 2019-04-05 | 镇江利德尔复合材料有限公司 | A kind of preparation method for the vector resin that refractory molded technique coloured material uses |
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| CN102432854A (en) * | 2011-08-31 | 2012-05-02 | 常州天马集团有限公司 | Polyester plasticizer for leading glass fiber to form felt and preparation method of polyester plasticizer |
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| CN102432854A (en) * | 2011-08-31 | 2012-05-02 | 常州天马集团有限公司 | Polyester plasticizer for leading glass fiber to form felt and preparation method of polyester plasticizer |
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