CN1044667A - Unsaturated polyester resin mixed liquid and preparation technology - Google Patents
Unsaturated polyester resin mixed liquid and preparation technology Download PDFInfo
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- CN1044667A CN1044667A CN 89105227 CN89105227A CN1044667A CN 1044667 A CN1044667 A CN 1044667A CN 89105227 CN89105227 CN 89105227 CN 89105227 A CN89105227 A CN 89105227A CN 1044667 A CN1044667 A CN 1044667A
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Abstract
The invention discloses a kind of unsaturated polyester resin mixed liquid and preparation technology.It is to be raw material with oil, formaldehyde, unsaturated dibasic acid or acid anhydrides, monounsaturated dicarboxylic acid or acid anhydrides and dibasic alcohol at the bottom of the tower, after the polycondensation, adds cross-linking monomer, stopper, release agent and other properties-correcting agent, just can obtain resin mixture liquor of the present invention.The present invention can be applied to aspects such as anticorrosive, mold pressing, casting, hand paste, stratified plastics, coating.It is good to have non-corrosibility, and viscosity is little, and wetting property is good, and working life is long, and application property is good, and shrinking percentage is little, characteristics such as FRP physical strength height.
Description
The present invention is a kind of unsaturated polyester resin mixed liquid and preparation technology.In more detail, it is with petroleum refining aromatic hydrocarbons (benzene,toluene,xylene, trimethylbenzene) afterwards, fraction between 170～250 ℃ (abbreviate as tower at the bottom of oil) is raw material, with unsaturated dibasic acid or acid anhydrides, unsaturated polyester resin mixed liquid and preparation technology that monounsaturated dicarboxylic acid or acid anhydrides and dibasic alcohol generate through the reaction of two steps.The present invention can be applied to impregnating material, castable plastic, moulded plastics, the hand of matrix and stick with paste aspects such as plastics, stratified plastics, coating and tackiness agent.Characteristics such as it has that viscosity is little, wetting property good, the cycle that is suitable for is long, application property good, shrinking percentage is little when solidifying.
At present, the unsaturated polyester resin kind of domestic production, the trade mark are a lot of, but its difference mainly is selected starting monomer difference, or in the mixing acid component, unsaturated acid is different with the ratio of saturated acid, or the mode difference that feeds intake, thus, synthesized unsaturated polyester resin, be applicable to industrial different needs with different performance.
It is raw material that common people adopt dimethylbenzene, acid is catalyzer, with formaldehyde reaction, obtains dimethylbenzene one formaldehyde resin, and then employing dimethylbenzene one formaldehyde resin is raw material and unsaturated dibasic acid or acid anhydrides, monounsaturated dicarboxylic acid or acid anhydrides and diol reaction, the preparation unsaturated polyester uses for industry, its shortcoming has been to use chemical reagent dimethylbenzene as raw material, supply falls short of demand to have caused chemical reagent, improved cost, makes to produce to be restricted.
It is raw material that people also can adopt dihydroxyphenyl propane, preparation unsaturated polyester or employing low-molecular-weight epoxy resin, preparation vinyl unsaturated polyester resin.Its shortcoming is that raw material is in short supply, and the product price height can not satisfy industrial heavy demand.
Along with developing rapidly of China Petroleum, the degree of depth refining capacity of petroleum industry improves constantly.Oil is refining aromatic hydrocarbons (benzene,toluene,xylene, trimethylbenzene) afterwards, and the fraction between 170～250 ℃ is because the component complexity can not can not act as a fuel as solvent.Oil is when burning at the bottom of the tower, because incomplete combustion, smog is big, causes serious environmental to pollute.Therefore, oil fails to obtain comprehensive utilization so far at the bottom of the tower.China's oil that is richly stored with, petroleum industry urgently will be carried out comprehensive development and utilization to oil at the bottom of the tower.
The objective of the invention is to overcome the shortcoming of above-mentioned prior art, provide a kind of chemical reagent dimethylbenzene that do not adopt as raw material, thereby both can reduce cost, can not be subjected to the deficiency of chemical reagent again, and limit the production of unsaturated polyester resin.
Another object of the present invention is to be not adopt the price height, and therefore originate dihydroxyphenyl propane and low-molecular-weight epoxy resin in short supply reduce cost.
Another purpose of the present invention be adopt the tower of petroleum industry at the bottom of oil as raw material, can not only make a large amount of towers at the bottom of oil obtained comprehensive utilization, opened up the source of novel material, sufficient raw, reduced cost, and by chemical reaction, the unsaturated polyester resin viscosity that synthesizes is little, wetting property is good, working life is long, and application property is good, corrosion resistance and good, the physical strength height of FRP, excellent performance.
In order to achieve the above object, unsaturated polyester resin mixed liquid of the present invention comprises that with oil, formaldehyde, unsaturated dibasic acid or acid anhydrides, monounsaturated dicarboxylic acid or acid anhydrides and dibasic alcohol at the bottom of the tower be raw material, through the reaction of two steps, prepare unsaturated polyester resin, add cross-linking monomer (thinner) vinylbenzene, hydroquinone of polymerization retarder, release agent paraffin and other properties-correcting agent.
Resin is to contain oil at the bottom of the tower, aldehyde compound in the middle of of the present invention, and mineral acid is catalyzer resin in the middle of addition reaction gets.Its mass fraction is: oil is reinforced with any ratio with aldehyde compound at the bottom of the tower, oil at the bottom of the tower: mineral acid=1: 0.05～0.5.
The present invention adopts the fraction behind the petroleum refining aromatic hydrocarbons, for example oil at the bottom of the tower.
The present invention adopts any of aldehyde compound and combination, for example formalin.
The catalyzer that the present invention adopts is the muriate of inorganic acids compound or tin, for example concentrated hydrochloric acid, tin trichloride etc.
Unsaturated polyester resin of the present invention is a resin in the middle of containing, unsaturated dibasic acid or acid anhydrides, and monounsaturated dicarboxylic acid or acid anhydrides and dibasic alcohol are through the unsaturated polyester resin of polycondensation preparation.Its mass fraction (mol ratio) is (middle resin+dibasic alcohol): (unsaturated dibasic acid or acid anhydrides+monounsaturated dicarboxylic acid or acid anhydrides)=(0.5-1.5): 1, resin and two dibasic alcohol are any ratios wherein, and unsaturated dibasic acid or acid anhydrides and monounsaturated dicarboxylic acid or acid anhydrides also can be any ratios.
Unsaturated polyester resin mixed liquid of the present invention is to contain cross-linking monomer (thinner) vinylbenzene, hydroquinone of polymerization retarder, release agent paraffin and other various properties-correcting agent, for example filler, dyestuff, lubricant, softening agent, toughner etc.
The cross-linking monomer (thinner) that the present invention adopts is a vinylbenzene, also can be methyl methacrylate, diallyl phthalate, cyanuric acid tripropylene etc.
The stopper that the present invention adopts is a Resorcinol, also can be quinhydrones etc.
The release agent that the present invention adopts is a hydrocarbon compound, for example paraffin etc.
In addition, the present invention can add other various properties-correcting agent according to concrete purposes, for example, and filler, dyestuff, lubricant, softening agent, toughner etc.
Purpose of the present invention can reach by following measure, i.e. the preparation method of unsaturated polyester resin mixed liquid of the present invention.
The first step addition reaction: add formalin in the reactor earlier, under agitation condition, drip concentrated hydrochloric acid, afterwards, drop into oil at the bottom of the tower again, its mass fraction is: oil can be reinforced with any ratio with aldehyde compound at the bottom of the tower, and oil at the bottom of the tower: mineral acid=1: 0.05～0.5, temperature of reaction are controlled at 85～150 ℃, reflux operation under the normal pressure, reacted 3～8 hours, stopped reaction feeds water vapor in reaction system, steam the oil content of not participating in reaction in the reactant, subsequently resin is separated with sour water, wash with water, resin in the middle of obtaining.
The reaction of second one-step polycondensation: in middle resin, add unsaturated dibasic acid or acid anhydrides, monounsaturated dicarboxylic acid or acid anhydrides and dibasic alcohol prepare unsaturated polyester resin through polycondensation.Its mass fraction (mole) is (middle resin+dibasic alcohol): (unsaturated dibasic acid or acid anhydrides+monounsaturated dicarboxylic acid or acid anhydrides)=(0.5～1.5): 1, resin and dibasic alcohol can be any ratios wherein, unsaturated dibasic acid or acid anhydrides also can be any ratios.Feed rare gas element in reactor, the air in the removal system under agitation condition, makes material temperature rise to 170～210 ℃, the atmospheric pressure reflux operation, and reaction 3～8h during control acid number 30～50mgKOH/g resin, stops heating, termination reaction.In the time of 90～110 ℃, add release agent paraffin, cross-linking monomer (thinner) vinylbenzene, treat that temperature is reduced to 70 ℃, add hydroquinone of polymerization retarder, after stirring, so just obtained unsaturated polyester resin mixed liquid of the present invention.
The unsaturated polyester resin mixed liquid that the present invention makes, outward appearance is brown transparent liquid, being coated with-4 glasss of mensuration viscosity numbers is under 25 ℃ of conditions, 31～35s, density is 1.04～1.07g/cm, the normal temperature storage phase can reach more than half a year.Therefore characteristics such as it is little that this resin mixture liquor has viscosity, and wetting property is good, and working life is long, and shrinking percentage is little during curing have customer satisfaction system application property.
It is that 360 ℃, compressive strength are that 156MPa, flexural strength are that 59MPa, tensile strength are that 14.4MPa, shock strength are 0.4j/cm that the second-order transition temperature of resin mixture liquor casting matrix of the present invention reaches 156 ℃, heat decomposition temperature
2The mechanical property that hand is stuck with paste FRP is as follows: notched Izod impact strength is 8j/cm
2, flexural strength is that 229MPa, compressive strength are that 138.8MPa, tensile strength are that 238MPa, resin mixture liquor casting matrix degree of cure are greater than 84%.
After unsaturated polyester resin mixed liquid of the present invention solidifies, good erosion resistance is arranged, ability is 40% left and right sides sodium hydroxide solution below 70 ℃; Below 90 ℃, the sulphuric acid soln of ability below 70%, 30% chromic acid, hydrofluoric acid, salpeter solution, about 15% hydrochloric acid soln, concentrated salt solution, ability concentrated ammonia solution under the normal temperature.
The resin mixture liquor that the present invention makes, can be as corrosion resistant material under the high temperature, transport the pipeline of strong corrosive medium, storage tank, basin, pickling tank, the plating tank of storage strong corrosive medium as manufacturing, also can be used as the building anti-corrosion material, except that above-mentioned special purpose, has the identical purposes of similar resin.
Unsaturated polyester resin mixed liquid embodiment of the present invention is as follows: (following is mass ratio)
Embodiment 1
Take by weighing technical grade formalin (more than 36%) 10g, under the agitation condition, drip concentrated hydrochloric acid 4g, afterwards, drop into oil at the bottom of the 12g tower again, constantly stir, be warmed up to 120 ℃, atmospheric pressure reflux operation, reaction 5h, stopped reaction, feed in the reaction system with water vapor, steam unreacted oil content, resin is separated with sour water, wash the acid in the resin with water, resin in the middle of can obtaining.
Resin 10g, 1 in the middle of taking by weighing, 2-propylene glycol 3g, glycol ether 1g, MALEIC ANHYDRIDE 5g, Tetra hydro Phthalic anhydride 2g, after feeding intake, feed nitrogen, the air in the removal system is warmed up to 170～200 ℃ gradually, reaction 5h, the control acid number is 30～50mgKOH/g resin, stops heating, termination reaction.When temperature is reduced to 90～110 ℃, add cross-linking monomer (thinner) vinylbenzene 12g and release agent paraffin trace, treat that temperature is reduced to 70 ℃ and adds the hydroquinone of polymerization retarder trace.Discharging after stirring just can obtain unsaturated polyester resin mixed liquid of the present invention.
Above-mentioned resulting unsaturated polyester resin mixed liquid is brown transparent liquid, and being coated with-4 glasss of mensuration viscosity numbers is 31～35s, and density is 1.04～1.07g/cm
3, the normal temperature storage phase can reach more than half a year.It is little that this resin mixture liquor has viscosity, and wetting property is good, and can have good application property working life at 2h～3h, and shrinking percentage is little during curing.
Embodiment 2
Take by weighing technical grade formalin (more than 36%) 50g, under the agitation condition, drip concentrated hydrochloric acid 25g, afterwards, drop into oil 70g at the bottom of the tower again, be warmed up to 120 ℃.Under the agitation condition, the atmospheric pressure reflux operation, reaction 5h, stopped reaction feeds water vapor in reaction system, steam unreacted oil content, and resin is separated with sour water, washes the acid in the resin with water, resin in the middle of obtaining.
Resin 50g in the middle of taking by weighing, 1,2-propylene glycol 17g, glycol ether 6g, MALEIC ANHYDRIDE 30g, Tetra hydro Phthalic anhydride 12g, drop into together, feed the air in nitrogen, the removal system, be warmed up to 170～200 ℃ gradually, reaction 7h, the control acid number is 30～50mgKOH/g resin, stops heating, termination reaction.Add release agent paraffin 0.3g when temperature is reduced to 90～110 ℃, cross-linking monomer vinylbenzene 66g treats that temperature is reduced to 70 ℃ and adds hydroquinone of polymerization retarder 0.9g, and the back discharging that stirs just can obtain unsaturated polyester resin mixed liquid of the present invention.
The result of use of embodiment 2 is substantially the same manner as Example 1.
Embodiment 3
Take by weighing technical grade formalin 100g, under the agitation condition, drip concentrated hydrochloric acid 40g, oil at the bottom of the input tower is warmed up to 120 ℃, and insulation 5h is stirred in the atmospheric pressure reflux operation.Stopped reaction.In reaction system, feed water vapor, steam unreacted oil content, resin is separated with sour water, wash the acid in the resin with water, resin in the middle of obtaining.
Resin 100g in the middle of taking by weighing, 1,2 one propylene glycol 35g, glycol ether 10g, MALEIC ANHYDRIDE 50g, Tetra hydro Phthalic anhydride 25g, feed intake together, feed nitrogen, the air in the removal system, be warmed up to 170～200 ℃ gradually, reaction 7h, the control acid number is 30～50mgKOH/g resin, stops heating, termination reaction, when temperature is reduced to 90～110 ℃, add release agent paraffin 0.6g, cross-linking monomer vinylbenzene 130g, treat that temperature is reduced to 70 ℃, add hydroquinone of polymerization retarder 1.8g.After stirring, discharging just can obtain unsaturated polyester resin mixed liquid.
The result of use of embodiment 3 is substantially the same manner as Example 1.
Claims (11)
1, resin in the middle of a kind of is characterized in that containing oil at the bottom of the tower, aldehyde compound, and the inorganic acids compound is made catalyzer, and its mass fraction is: oil is any ratio with aldehyde compound at the bottom of the tower, oil at the bottom of the tower: mineral acid=1: 0.05～0.5.
2, resin in the middle of according to claim 1 is characterized in that oil at the bottom of its said tower is the fraction behind the petroleum refining aromatic hydrocarbons.
3, resin in the middle of according to claim 1, it is characterized in that it said be any and combination, for example formalin of aldehyde compound.
4, resin in the middle of according to claim 1 is characterized in that it being the muriate of any and combination or tin of inorganic acids compound, for example concentrated hydrochloric acid, tin trichloride etc.
5, a kind of unsaturated polyester resin, it is characterized in that containing middle resin, unsaturated dibasic acid or acid anhydrides, monounsaturated dicarboxylic acid or acid anhydrides, reach dibasic alcohol, its mass fraction is (middle resin+dibasic alcohol): (unsaturated dibasic acid or acid anhydrides+monounsaturated dicarboxylic acid or acid anhydrides)=0.5-1.5 mole: 1 mole.Wherein unsaturated dibasic acid or acid anhydrides and monounsaturated dicarboxylic acid or acid anhydrides can be any mass ratios, and middle resin and dibasic alcohol also can be any ratios.
6, a kind of unsaturated polyester resin mixed liquid is characterized in that it being to contain cross-linking monomer (thinner), stopper, release agent and other various properties-correcting agent, for example filler, dyestuff, lubricant, softening agent, toughner etc.
7, unsaturated polyester resin mixed liquid according to claim 6 is characterized in that cross-linking monomer (thinner) is a vinylbenzene, also can be methyl methacrylate, diallyl phthalate, cyanuric acid tripropylene etc.
8, unsaturated polyester resin mixed liquid according to claim 6 is characterized in that stopper is a Resorcinol, also can be quinhydrones etc.
9, unsaturated polyester resin mixed liquid according to claim 6 is characterized in that release agent is a hydrocarbon compound, for example paraffin etc.
10, unsaturated polyester resin mixed liquid according to claim 6 is characterized in that adding other various properties-correcting agent, for example filler, dyestuff, lubricant, softening agent, toughner etc.
11, a kind of preparation method of unsaturated polyester resin mixed liquid is characterized in that:
(1) add aldehyde compound in the reactor earlier, under the agitation condition, the dropping inorganic acid class adds oil at the bottom of the tower afterwards, and its mass fraction is an oil at the bottom of the tower: mineral acid=1: 0.05～0.5.
(2) temperature of reaction is controlled at 85～105 ℃, reflux operation under the normal pressure, reaction 3～8h, termination reaction.
(3) in reaction system, feed water vapor, steam the oil content of not participating in reaction in the reactant, resin is separated with sour water, wash resin with water, resin in the middle of obtaining.
(4) in middle resin, add unsaturated dibasic acid or acid anhydrides, monounsaturated dicarboxylic acid or acid anhydrides and dibasic alcohol, prepare unsaturated polyester resin through polycondensation, feed rare gas element, under the agitation condition, be warming up to 170～210 ℃, the atmospheric pressure reflux operation, reaction 3～8h, the control acid number is 30～50mgKOH/g resin, termination reaction.
(5) add release agent paraffin, cross-linking monomer (thinner) vinylbenzene, hydroquinone of polymerization retarder and other various properties-correcting agent in the unsaturated polyester resin in reactor, for example filler, dyestuff, lubricant, softening agent, toughner etc. stir, and make stable uniform unsaturated polyester resin mixed liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89105227 CN1030612C (en) | 1989-02-01 | 1989-02-01 | Unsaturated polyester resin mixed liquid and preparation process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89105227 CN1030612C (en) | 1989-02-01 | 1989-02-01 | Unsaturated polyester resin mixed liquid and preparation process thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1044667A true CN1044667A (en) | 1990-08-15 |
| CN1030612C CN1030612C (en) | 1996-01-03 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89105227 Expired - Fee Related CN1030612C (en) | 1989-02-01 | 1989-02-01 | Unsaturated polyester resin mixed liquid and preparation process thereof |
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| Country | Link |
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| CN (1) | CN1030612C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206309A (en) * | 2011-04-18 | 2011-10-05 | 广东同步化工股份有限公司 | Thermosetting acrylic resin for electrogilding oil and preparation method thereof |
| CN112745649A (en) * | 2020-12-29 | 2021-05-04 | 江苏恒力化纤股份有限公司 | Preparation method of unsaturated polyester-based composite material for surfboards |
-
1989
- 1989-02-01 CN CN 89105227 patent/CN1030612C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206309A (en) * | 2011-04-18 | 2011-10-05 | 广东同步化工股份有限公司 | Thermosetting acrylic resin for electrogilding oil and preparation method thereof |
| CN102206309B (en) * | 2011-04-18 | 2012-12-12 | 广东同步化工股份有限公司 | Thermosetting acrylic resin for electrogilding oil and preparation method thereof |
| CN112745649A (en) * | 2020-12-29 | 2021-05-04 | 江苏恒力化纤股份有限公司 | Preparation method of unsaturated polyester-based composite material for surfboards |
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| Publication number | Publication date |
|---|---|
| CN1030612C (en) | 1996-01-03 |
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