CN103755938A - High-ductility unsaturated polyester resin under low-temperature environment - Google Patents
High-ductility unsaturated polyester resin under low-temperature environment Download PDFInfo
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- CN103755938A CN103755938A CN201410004739.XA CN201410004739A CN103755938A CN 103755938 A CN103755938 A CN 103755938A CN 201410004739 A CN201410004739 A CN 201410004739A CN 103755938 A CN103755938 A CN 103755938A
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Abstract
The invention relates to high-ductility unsaturated polyester resin under a low-temperature environment and a synthetic method and application thereof. The high-ductility unsaturated polyester resin under a low-temperature environment provided by the invention is linear chain unsaturated polyester resin; the viscosity, measured by a vertebral plate viscosity meter, of the resin is 2cps-20cps (125 DEG C) and the weight-average molecular weight of the resin is 20,000-100,000. The high-ductility unsaturated polyester resin is obtained by carrying out a polymerization reaction on the following components through a polymerization inhibitor and a tin type catalyst: one or more conjugated vinyl unsaturated binary acid (A) with the mol amount of 5%-30%, one or more of aliphatic series or aromatic series binary acid (B) with the mol amount of 20%-45% and two or more of polyhydric alcohols (C) with the mol amount of 40%-60%; the maximum ductility of a cured product under the environment of 20 DEG C is 150%-460% and is 20%-460% under the environment of -20 DEG C; the unsaturated polyester resin can be used for producing a weather-resisting product used in the environment of 0 DEG C below. In the application, the resin has very good flexibility at room temperature and is very good in adhesion with a supporting material, particularly under the environment with low-temperature requirements.
Description
Technical field
The present invention relates to unsaturated polyester resin, especially high-elongation unsaturated polyester resin under low temperature environment, to be applicable to weathering resistance unsaturated polyester resin of using compared with the adhesive for concrete of high-flexibility requirement and terrace etc., the invention still further relates in addition the preparation method of described unsaturated polyester resin.
Technical background
Flexible unsaturated polyester resin as coating, waterproof and sealing use is normally made by di-carboxylic acid, polypropylene oxide or polyethylene oxide.For making resin have curing performance under general superoxide or the existence of other radical initiator, part acid must be unsaturated acid.
The subject matter that unsaturated polyester resin product in the past exists is just to have high water absorbing capacity, this is the reason that causes product to decline at the lower flexural strength of room temperature and low temperature environment (20 ℃) and unit elongation, is also to cause product snappiness to reduce and the reason that has a strong impact on product stability.Therefore this just needs a kind of resin that can still can keep good snappiness and stability after solidifying under low-down temperature environment.
Summary of the invention
Object of the present invention is just to provide high-elongation unsaturated polyester resin under a kind of low temperature environment, to meet, still has better snappiness and weathering resistance below zero degrees celsius environment.
Another object of the present invention is to provide the preparation method of high-elongation unsaturated polyester resin under described low temperature environment.
A further object of the present invention is: the purposes of high-elongation unsaturated polyester resin under the low temperature environment described in providing.
The object of the invention is achieved through the following technical solutions: high-elongation unsaturated polyester resin under a kind of low temperature environment, for linear chain unsaturated polyester resin, its viscosity recording under the sticky meter of vertebral plate is 2cps～20cps (125 ℃), weight-average molecular weight is 20.000-100.000, by comprising that following component urges agent polyreaction to obtain by stopper and tin class:
One or more conjugation vinyl unsaturated dibasic acid (A) 5～30% molar weights
One or more aliphatics or aromatic acid (B) 20～45% molar weights
Two or more polyvalent alcohol (C) 40～60% molar weights,
The maximum unit elongation of product after solidifying under 20 ℃ of environment is 150～460%, under-20 ℃ of environment, is 20-460%, wherein,
Described conjugation vinyl unsaturated dibasic acid (A) is toxilic acid, maleic anhydride or fumaric acid;
Described aliphatics or aromatic acid diprotic acid (B) are phthalic acid, Tetra hydro Phthalic anhydride, m-phthalic acid or terephthalic acid;
Described polyvalent alcohol (C) is triglycol, dipropylene glycol, three polypropylene glycols, dihydroxyphenyl propane, trimethylolethane, TriMethylolPropane(TMP), polyoxyethylene glycol or derivatives thereof, glycol polypropylene or derivatives thereof, and its molecular weight is 400～1500;
Described metal species catalyzer is;
Described stopper is Resorcinol, toluhydroquinone, single Tert. Butyl Hydroquinone, di-tert-butyl hydroquinone or tri-tert Resorcinol.
The following snappiness of resistance to chemical attack, weathering resistance, zero degrees celsius that unsaturated polyester resin of the present invention has had at needs, water tolerance, high impact resistance.
On such scheme basis, the viscosity number that under described low temperature environment, high-elongation unsaturated polyester resin records at vertebral plate viscometer is 5ps～15ps (125 ℃), and weight-average molecular weight is 40000-100000.
Further, the each component of the present invention is:
Conjugation vinyl unsaturated dibasic acid (A) 10～20% molar weights of described one or more
The aliphatics of described one or more or aromatic acid (B) 30～40% molar weights
Polyvalent alcohol (C) 45～55% molar weights of described two or more.
The preparation method who the invention provides high-elongation unsaturated polyester resin under a kind of low temperature environment, comprises the steps:
Step 1, takes in following component placing response still by formula ratio:
One or more conjugation vinyl unsaturated dibasic acid (A) 5～30% molar weights;
One or more aliphatics or aromatic acid (B) 20～45% molar weights;
Two or more polyvalent alcohol (C) 40～60% molar weights;
Step 2 progressively heats up in reactor, and adds stopper and tin metalloid catalyzer, until acid number is 5～35mgKOH/g, obtains linear polyester, then, dilutes with one or more reactive monomer of 30%～60% massfraction.Be used for producing the unsaturated polyester resin base product with snappiness and weather condition under zero degree with the resin that aforesaid method obtains.
On aforesaid method basis, conjugation vinyl unsaturated dibasic acid (A) 10～20% molar weights, one or more aliphatics or aromatic acid (B) 30～40% molar weights, two or more polyvalent alcohol (C) 45%～55% molar weight with one or more are reacted, until acid number is less than 20mgKOH/g, obtain required linear polyester, then, with the reactive monomer of 35～55% massfractions, dilute.
On aforesaid method basis, when reaction proceeds to acid number lower than 10mgKOH/g, meanwhile, its cone-plate and dull and stereotyped viscosity number are during higher than 10cps/125 ℃, and reaction completes.
Wherein, in step 1, one or more aliphatics or aromatic acid (B) and two or more polyvalent alcohol (C) first react, and then fill into one or more conjugation vinyl unsaturated dibasic acid (A), wherein, described conjugation vinyl unsaturated acid is divided into two portions, a part of conjugation vinyl unsaturated acid and other raw material reactions, and another part reacts with a part for other raw materials; Or, the conjugation vinyl unsaturated acid (A) of all one or more and starting raw material one are reacted.
The invention provides the purposes of high-elongation unsaturated polyester resin under described low temperature environment, for seal gum, insulating material, terrace resin, synthetic gel coat, synthetic paint, lining resin, filming agent, water-resistant resin or flexible resin sizing agent.
Further, product of the present invention be used for making concrete member seal gum, metal or concrete synthetic paint for coating, make lining resin, the ceramic adhering resin of liner, requirement has the reinforced plastics parts of better toughness as window membe etc., can be used for resin base glass fiber reinforced materials, can be suitable for the moulding processs such as sculpture, pultrusion and extruding.
Superiority of the present invention is: under described low temperature environment, high-elongation unsaturated polyester resin is after solidifying, and the elastic extension rate of testing under room temperature is not less than 90%, and is placed under-20 ℃ of environment, and the unit elongation of testing after boiling water bath boils 21 days is 50%.
Embodiment
Following instance is only for processing method of the invention process is described, these processing methodes exist a lot of variation within the scope of aim of the present invention and claim.
Example 1
The preparation of flexible unsaturated polyester resin A
By the m-phthalic acid of 0.4 mole of every massfraction, the polyoxypropyleneglycol of 0.4 mole of every massfraction, the polyoxytrimethylene trivalent alcohol of 0.1 mole of every massfraction joins and in reactor, carries out polyreaction, add metal catalyst simultaneously, preferably tin class catalyzer, until acid number drops to below 10mgKOH/g.Then cool to 100 ℃, add the maleic acid of 0.1 mole of every massfraction, then continue temperature reaction until acid number is down to below 20mgKOH/g.At 125 ℃ test hierarchy of control cone-plate viscosity number be 11.5PS. by gel permeation chromatography, to record number-average molecular weight be 7500, weight-average molecular weight is 78000.
Example 2
The application of flexible unsaturated polyester resin A
Linear unsaturated polyester Resin A in example 1 is diluted by adding 40% vinylbenzene, then with MEKP and the cobalt iso-octoate of 1%-2%, is cured.Final Young's modulus and other mechanical propertys are as shown in table 1:
Example 3
The application of flexible unsaturated polyester resin A
Linear unsaturated polyester Resin A in example 1 is diluted by adding 50% vinylbenzene, then with MEKP and the cobalt iso-octoate of 1%-2%, is cured, and under room temperature, through test, its Young's modulus is 460%.
The preparation of example 4 flexible unsaturated polyester resin B
By the m-phthalic acid of 0.4 mole of every massfraction, the polyoxypropyleneglycol of 0.4 mole of every massfraction, the polyoxytrimethylene trivalent alcohol of 0.1 mole of every massfraction joins and in reactor, carries out polyreaction, add metal catalyst simultaneously, preferably tin class catalyzer, until acid number will arrive below 25mgKOH/g.Then reaction system is cooled to 110 ℃, add the maleic acid of 0.1 mole of every massfraction, then continue temperature reaction until acid number is down to below 25mgKOH/g again.At 125 ℃ test hierarchy of control cone-plate viscosity number be 2.5-5.0PS. by gel permeation chromatography, to record number-average molecular weight be 3000, weight-average molecular weight is 20000.
Example 5
The preparation of flexible unsaturated polyester resin C
By the m-phthalic acid of 0.4 mole of every massfraction, the polyoxypropyleneglycol of 0.36 mole of every massfraction, the polyoxytrimethylene trivalent alcohol of 0.1 mole of every massfraction, the glycerol of 0.03 mole of every massfraction, the dihydroxyphenyl propane of 0.01 mole of every massfraction (pure or propoxy-), the maleic acid of 0.1 mole of every massfraction, above medicine or raw material join and in reactor, carry out polyreaction, add metal catalyst simultaneously, preferably tin class catalyzer, until acid number drops to below 40mgKOH/g.At 125 ℃ test hierarchy of control cone-plate viscosity number be 5.2PS. by gel permeation chromatography, to record number-average molecular weight be 2900, weight-average molecular weight is 25000.
Example 6
The application of flexible unsaturated polyester resin A and C
According in example 4 and example 5, this linear unsaturated polyester can add the vinylbenzene of about 35%-40%, then with MEKP and the cobalt iso-octoate of 1%-2%, is cured.By its mechanical property being tested to the relevant elastic mould value of final acquisition, table 2 is for by boiling water boiling measured result after 14 days, shown in table specific as follows:
Claims (9)
1. high-elongation unsaturated polyester resin under a low temperature environment, for linear chain unsaturated polyester resin, its viscosity recording under the sticky meter of vertebral plate is 2cps～20cps (125 ℃), weight-average molecular weight is 20.000-100.000, by comprising that following component urges agent polyreaction to obtain by stopper and tin class:
One or more conjugation vinyl unsaturated dibasic acid (A) 5～30% molar weights
One or more aliphatics or aromatic acid (B) 20～45% molar weights
Two or more polyvalent alcohol (C) 40～60% molar weights,
The maximum unit elongation of product after solidifying under 20 ℃ of environment is 150～460%, under-20 ℃ of environment, is 20-460%, wherein,
Described conjugation vinyl unsaturated dibasic acid (A) is toxilic acid, maleic anhydride or fumaric acid;
Described aliphatics or aromatic acid diprotic acid (B) are phthalic acid, Tetra hydro Phthalic anhydride, m-phthalic acid or terephthalic acid;
Described polyvalent alcohol (C) is triglycol, dipropylene glycol, three polypropylene glycols, dihydroxyphenyl propane, trimethylolethane, TriMethylolPropane(TMP), polyoxyethylene glycol or derivatives thereof, glycol polypropylene or derivatives thereof, and its molecular weight is 400～1500;
Described metal species catalyzer is;
Described stopper is Resorcinol, toluhydroquinone, single Tert. Butyl Hydroquinone, di-tert-butyl hydroquinone or tri-tert Resorcinol.
2. high-elongation unsaturated polyester resin under low temperature environment according to claim 1, is characterized in that, the viscosity number recording at vertebral plate viscometer is 5ps～15ps (125 ℃), and weight-average molecular weight is 40000-100000.
3. according to high-elongation unsaturated polyester resin under the low temperature environment described in claim 1 or 2, it is characterized in that:
Conjugation vinyl unsaturated dibasic acid (A) 10～20% molar weights of described one or more
The aliphatics of described one or more or aromatic acid (B) 30～40% molar weights
Polyvalent alcohol (C) 45～55% molar weights of described two or more.
4. according to the preparation method of high-elongation unsaturated polyester resin under the low temperature environment described in claims 1 to 3, comprise the steps:
Step 1, takes in following component placing response still by formula ratio:
One or more conjugation vinyl unsaturated dibasic acid (A) 5～30% molar weights;
One or more aliphatics or aromatic acid (B) 20～45% molar weights;
Two or more polyvalent alcohol (C) 40～60% molar weights;
Step 2 progressively heats up in reactor, and adds stopper and tin metalloid catalyzer, until acid number is 5～35mgKOH/g, obtains linear polyester, then, dilutes with one or more reactive monomer of 30%～60% massfraction.
5. the preparation method of high-elongation unsaturated polyester resin under low temperature environment according to claim 4, it is characterized in that: conjugation vinyl unsaturated dibasic acid (A) 10～20% molar weights, one or more aliphatics or aromatic acid (B) 30～40% molar weights, two or more polyvalent alcohol (C) 45%～55% molar weight with one or more are reacted, until acid number is less than 20mgKOH/g, obtain required linear polyester, then, with the reactive monomer of 35～55% massfractions, dilute.
6. according to the preparation method of high-elongation unsaturated polyester resin under the low temperature environment described in claim 4 or 5, it is characterized in that: when reaction proceeds to acid number lower than 10mgKOH/g, meanwhile, its cone-plate and dull and stereotyped viscosity number are during higher than 10cps/125 ℃, and reaction completes.
7. according to the preparation method of high-elongation unsaturated polyester resin under the low temperature environment described in claim 4 or 5, it is characterized in that: in step 1, one or more aliphatics or aromatic acid (B) and two or more polyvalent alcohol (C) first react, and then fill into one or more conjugation vinyl unsaturated dibasic acid (A), wherein, described conjugation vinyl unsaturated acid is divided into two portions, part conjugation vinyl unsaturated acid and other raw material reactions, another part reacts with a part for other raw materials; Or, the conjugation vinyl unsaturated acid (A) of all one or more and starting raw material one are reacted.
8. according to the purposes of high-elongation unsaturated polyester resin under the low temperature environment described in claims 1 to 3, it is characterized in that: for seal gum, insulating material, terrace resin, synthetic gel coat, synthetic paint, lining resin, filming agent, water-resistant resin or flexible resin sizing agent.
9. the purposes of high-elongation unsaturated polyester resin under low temperature environment according to claim 8, it is characterized in that: be used for making concrete member seal gum, metal or concrete synthetic paint for coating, make lining resin, the ceramic adhering resin of liner, window membe, for sculpture, pultrusion and extruding shaping technique.
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| CN201410004739.XA CN103755938A (en) | 2014-01-06 | 2014-01-06 | High-ductility unsaturated polyester resin under low-temperature environment |
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| CN201410004739.XA CN103755938A (en) | 2014-01-06 | 2014-01-06 | High-ductility unsaturated polyester resin under low-temperature environment |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107099227A (en) * | 2017-05-17 | 2017-08-29 | 恒昌涂料（惠阳）有限公司 | The unsaturated polyester resin of solid content 100% and the net taste PE varnish of low VOC |
| CN108276530A (en) * | 2018-01-12 | 2018-07-13 | 宜兴市兴合树脂有限公司 | The high intensity drawing and extruding section bar resin of resisting sea water erosion |
| CN109369895A (en) * | 2018-09-15 | 2019-02-22 | 福建省南安市华龙树脂有限公司 | A kind of unsaturated polyester resin and preparation method thereof for antifreezing coat |
| CN113912812A (en) * | 2021-10-22 | 2022-01-11 | 东莞市米儿塑胶原料有限公司 | Preparation method of degradable TPU (thermoplastic polyurethane) based on recycled PET (polyethylene terephthalate) |
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| CN1320133A (en) * | 1998-09-29 | 2001-10-31 | 奈斯特化学公司 | Unsaturated polyester resin and the use of it |
| CN101805429A (en) * | 2010-03-18 | 2010-08-18 | 上海新天和树脂有限公司 | Flexible unsaturated polyester resin and preparation method and application thereof |
| CN103289068A (en) * | 2013-05-21 | 2013-09-11 | 山东宏信化工股份有限公司 | Preparation method of glycerinum modified unsaturated polyester resin |
| CN103396540A (en) * | 2013-07-22 | 2013-11-20 | 南通天和树脂有限公司 | Flexible unsaturated polyester resin |
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2014
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1320133A (en) * | 1998-09-29 | 2001-10-31 | 奈斯特化学公司 | Unsaturated polyester resin and the use of it |
| CN101805429A (en) * | 2010-03-18 | 2010-08-18 | 上海新天和树脂有限公司 | Flexible unsaturated polyester resin and preparation method and application thereof |
| CN103289068A (en) * | 2013-05-21 | 2013-09-11 | 山东宏信化工股份有限公司 | Preparation method of glycerinum modified unsaturated polyester resin |
| CN103396540A (en) * | 2013-07-22 | 2013-11-20 | 南通天和树脂有限公司 | Flexible unsaturated polyester resin |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107099227A (en) * | 2017-05-17 | 2017-08-29 | 恒昌涂料（惠阳）有限公司 | The unsaturated polyester resin of solid content 100% and the net taste PE varnish of low VOC |
| CN107099227B (en) * | 2017-05-17 | 2019-07-05 | 恒昌涂料（惠阳）有限公司 | 100% unsaturated polyester resin of solid content and low VOC ordor removing PE varnish |
| CN108276530A (en) * | 2018-01-12 | 2018-07-13 | 宜兴市兴合树脂有限公司 | The high intensity drawing and extruding section bar resin of resisting sea water erosion |
| CN109369895A (en) * | 2018-09-15 | 2019-02-22 | 福建省南安市华龙树脂有限公司 | A kind of unsaturated polyester resin and preparation method thereof for antifreezing coat |
| CN109369895B (en) * | 2018-09-15 | 2021-02-09 | 福建省南安市华龙树脂有限公司 | Unsaturated polyester resin for anti-freezing coating and preparation method thereof |
| CN113912812A (en) * | 2021-10-22 | 2022-01-11 | 东莞市米儿塑胶原料有限公司 | Preparation method of degradable TPU (thermoplastic polyurethane) based on recycled PET (polyethylene terephthalate) |
| CN113912812B (en) * | 2021-10-22 | 2023-01-17 | 东莞市米儿塑胶原料有限公司 | Preparation method of degradable TPU (thermoplastic polyurethane) based on recycled PET (polyethylene terephthalate) |
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Application publication date: 20140430 |