CN105199327B - A kind of large-scale Plumbic acid accumulator container vinylite and preparation method thereof - Google Patents

A kind of large-scale Plumbic acid accumulator container vinylite and preparation method thereof Download PDF

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CN105199327B
CN105199327B CN201510629230.9A CN201510629230A CN105199327B CN 105199327 B CN105199327 B CN 105199327B CN 201510629230 A CN201510629230 A CN 201510629230A CN 105199327 B CN105199327 B CN 105199327B
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vinylite
parts
raw material
reacted
scale
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CN105199327A (en
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许曼
金鑫
杜灵根
王姗姗
朱宏
王晓梅
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HUBEI GREATSEA NEWPOWER TECHNOLOGY Co Ltd
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HUBEI GREATSEA NEWPOWER TECHNOLOGY Co Ltd
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Abstract

The invention discloses a kind of large-scale Plumbic acid accumulator container vinylite, contains imine group by 50 parts of vinylite, 5-15 parts of curing agent, 2.5-10 parts of accelerator, 15-20 parts of compositions of 2.5 parts of defoamer and diluent, described vinylite；Also disclose its preparation method, using THPA and monoethanolamine as raw material, it is reacted that imidohydrine is first made, again using maleic anhydride and imidohydrine as raw material, reacted obtained maleic acid imines ester, it is reacted that the vinylite with imine group is made finally using maleic acid imines ester and bisphenol A type epoxy resin as raw material.The vinylite moulding material of preparation has the characteristics that acid resistance is good, heat-resist and excellent in mechanical performance.By test, moulding material bending strength is 150MPa, tensile strength 98MPa, compressive strength 138MPa, and heat distortion temperature is 135 DEG C, and cure shrinkage is 4.5%.

Description

A kind of large-scale Plumbic acid accumulator container vinylite and preparation method thereof
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of large-scale Plumbic acid accumulator container is with vinyl tree Fat, with and preparation method thereof.
Background technology
At present no matter international or domestic lead-acid accumulator battery case, be made mostly of plastics such as PVC, ABS, PP, It can be very good to play using battery performance at normal temperatures, but can be declined rapidly using battery performance at high temperature, main cause It is that, in hot environment and compared with high internal pressure, battery case exists larger because the modulus of elasticity of above material, intensity are relatively low Deformation, outwards heaves.
Vinylite had both remained the basic chain of epoxy resin as internationally recognized height corrosion-resistant resin in molecule Section, and there is unsaturated double-bond at both ends, obtained widely with its excellent corrosion resistance, mechanical performance and good manufacturability Using having recently become the optimal matrix resin for producing large-scale Plumbic acid accumulator container.
The content of the invention
An object of the present invention is to be directed to existing deficiency, there is provided it is a kind of that not only there is good heat resistance, and have There are preferable mechanical property and acid proof large-scale Plumbic acid accumulator container vinylite.
The technical solution adopted for the present invention to solve the technical problems is：A kind of large-scale Plumbic acid accumulator container is with vinyl tree Fat, the raw material matched by following parts by weight are formed：50 parts of vinylite, 5-15 parts of curing agent, 2.5-10 parts of accelerator, 15-20 parts of 2.5 parts of defoamer and diluent, described vinylite contain imine group.
A kind of described large-scale Plumbic acid accumulator container vinylite, its curing agent are methyl ethyl ketone peroxide or peroxidating Cyclohexanone or benzoyl peroxide.
A kind of described large-scale Plumbic acid accumulator container vinylite, its accelerator be cobalt naphthenate or cobalt iso-octoate or Dimethylaniline.
A kind of described large-scale Plumbic acid accumulator container vinylite, its defoamer are BYK-A515.
A kind of described large-scale Plumbic acid accumulator container vinylite, its diluent are styrene or styrene-ethylene Base toluene mixture.
The second object of the present invention is to provide the preparation method of vinylite.
The technical solution adopted for the present invention to solve the technical problems is：A kind of large-scale Plumbic acid accumulator container is with vinyl tree The preparation method of fat, comprises the following steps
a）, using THPA and monoethanolamine as raw material, reacted that imidohydrine is first made, reaction equation is as follows
Wherein, R is
；
b）, using maleic anhydride and imidohydrine as raw material, reacted obtained maleic acid imines ester, reaction equation It is as follows
；
c）, using maleic acid imines ester and bisphenol A type epoxy resin as raw material, it is reacted be made the second with imine group Ene based resins, reaction equation are as follows
Wherein, R ' is
。
A kind of preparation method of described large-scale Plumbic acid accumulator container vinylite, its step a）In THPA Dosage mol ratio with monoethanolamine is 1:1, reaction temperature is 80-100 DEG C, N2Protection, reaction time are 8 hours.
A kind of preparation method of described large-scale Plumbic acid accumulator container vinylite, its step b）In maleic two The dosage mol ratio of acid anhydrides and imidohydrine is 1:1, sulphuric acid catalysis, reaction temperature is 60 DEG C, and the reaction time is 4 hours.
A kind of preparation method of described large-scale Plumbic acid accumulator container vinylite, its step c）In maleic two The dosage mol ratio of acid imide ester and bisphenol A type epoxy resin is 2:1, reaction temperature is 120-140 DEG C, catalyst used Catalyst used by being esterified for epoxy ring-opening, polymerization inhibitor used are to prevent from hindering used by free yl polymerizating monomer polymerization Poly- agent, reaction time are 4-6 hours, treat that temperature is down to less than 80 DEG C, vinylite is dissolved in into diluent.
The beneficial effects of the present invention are：Polyester-imide group is incorporated into vinyl by the present invention with the method for MOLECULE DESIGN In resin, the heat resistance after resin solidification is improved, while there is excellent acid resistance and mechanical property, is completely suitable for big Type Plumbic acid accumulator container is used；Meanwhile category of the vinylite as unsaturated polyester resin, activity is high, and curing rate is fast, with Unsaturated polyester resin is the same along with obvious volume contraction；The vinylite moulding material of preparation have acid resistance it is good, The features such as heat-resist and excellent in mechanical performance.By test, moulding material bending strength is 150MPa, and tensile strength is 98MPa, compressive strength 138MPa, heat distortion temperature are 135 DEG C, and cure shrinkage is 4.5%.
Embodiment
The present invention is described in further detail with reference to embodiment.
Embodiment 1
THPA is put into reactor, starts stirring, N2Protection, add the monoethanolamine of equimolar amounts, closing charging Mouthful, control temperature is at 80-100 DEG C, and in 8 hours reaction time, acid value is blanking in 0.5-5.0mgKOH/g.
By equimolar than imidohydrine and maleic anhydride input reactor, sulphuric acid catalysis, 60 DEG C of reaction temperature, instead 4 hours between seasonable, generate maleic acid imines ester.
Maleic acid imines ester is put into reactor, is warming up to 80 DEG C, adds benzyl dimethylamine and hydroquinones, point Not Zuo Wei catalyst and polymerization inhibitor use, bisphenol A type epoxy resin, maleic acid imines ester and bisphenol-A type ring is added portionwise The dosage mol ratio of oxygen tree fat is 2:1, be warming up to 120-140 DEG C, 4-6 hours reaction time, acid number control 10- 15mgKOH/g, the as vinylite with imine group, treat that temperature is down to less than 80 DEG C, and vinylite is dissolved in into dilution Agent.
Resin is prepared in proportion, wherein 50 parts of the vinylite containing imine group；5 parts of methyl ethyl ketone peroxide；Cycloalkanes Sour 2.5 parts of cobalt；2.5 parts of BYK-A515 defoamers；15 parts of styrene.
The vinylite moulding material of preparation has the characteristics that acid resistance is good, heat-resist and excellent in mechanical performance.Through Test is crossed, moulding material bending strength is 150MPa, tensile strength 98MPa, compressive strength 138MPa, and heat distortion temperature is 135 DEG C, and cure shrinkage is 4.5%.
Embodiment 2
THPA is put into reactor, starts stirring, N2Protection, add the monoethanolamine of equimolar amounts, closing charging Mouthful, control temperature is at 80-100 DEG C, and in 8 hours reaction time, acid value is blanking in 0.5-5.0mgKOH/g.
By equimolar than imidohydrine and maleic anhydride input reactor, sulphuric acid catalysis, 60 DEG C of reaction temperature, instead 4 hours between seasonable, generate maleic acid imines ester.
Maleic acid imines ester is put into reactor, is warming up to 80 DEG C, adds benzyl dimethylamine and hydroquinones, point Not Zuo Wei catalyst and polymerization inhibitor use, bisphenol A type epoxy resin, maleic acid imines ester and bisphenol-A type ring is added portionwise The dosage mol ratio of oxygen tree fat is 2:1, be warming up to 120-140 DEG C, 4-6 hours reaction time, acid number control 10- 15mgKOH/g, the as vinylite with imine group, treat that temperature is down to less than 80 DEG C, and vinylite is dissolved in into dilution Agent.
Resin is prepared in proportion, wherein 50 parts of the vinylite containing imine group；10 parts of methyl ethyl ketone peroxide；Ring 5 parts of alkanoic acid cobalt；2.5 parts of BYK-A515 defoamers；10 parts of styrene, 5 parts of vinyltoluene.
The cure shrinkage of vinylite can be reduced by making diluent from part vinyltoluene replacement styrene.
Embodiment 3
THPA is put into reactor, starts stirring, N2Protection, add the monoethanolamine of equimolar amounts, closing charging Mouthful, control temperature is at 80-100 DEG C, and in 8 hours reaction time, acid value is blanking in 0.5-5.0mgKOH/g.
By equimolar than imidohydrine and maleic anhydride input reactor, sulphuric acid catalysis, 60 DEG C of reaction temperature, instead 4 hours between seasonable, generate maleic acid imines ester.
Maleic acid imines ester is put into reactor, is warming up to 80 DEG C, adds benzyl dimethylamine and hydroquinones, point Not Zuo Wei catalyst and polymerization inhibitor use, bisphenol A type epoxy resin, maleic acid imines ester and bisphenol-A type ring is added portionwise The dosage mol ratio of oxygen tree fat is 2:1, be warming up to 120-140 DEG C, 4-6 hours reaction time, acid number control 10- 15mgKOH/g, the as vinylite with imine group, treat that temperature is down to less than 80 DEG C, and vinylite is dissolved in into dilution Agent.
Resin is prepared in proportion, wherein 50 parts of the vinylite containing imine group；10 parts of cyclohexanone peroxide；It is different 5 parts of cobalt octoate；2.5 parts of BYK-A515 defoamers；10 parts of styrene, 5 parts of vinyltoluene.
Embodiment 4
THPA is put into reactor, starts stirring, N2Protection, add the monoethanolamine of equimolar amounts, closing charging Mouthful, control temperature is at 80-100 DEG C, and in 8 hours reaction time, acid value is blanking in 0.5-5.0mgKOH/g.
By equimolar than imidohydrine and maleic anhydride input reactor, sulphuric acid catalysis, 60 DEG C of reaction temperature, instead 4 hours between seasonable, generate maleic acid imines ester.
Maleic acid imines ester is put into reactor, is warming up to 80 DEG C, adds benzyl dimethylamine and hydroquinones, point Not Zuo Wei catalyst and polymerization inhibitor use, bisphenol A type epoxy resin, maleic acid imines ester and bisphenol-A type ring is added portionwise The dosage mol ratio of oxygen tree fat is 2:1, be warming up to 120-140 DEG C, 4-6 hours reaction time, acid number control 10- 15mgKOH/g, the as vinylite with imine group, treat that temperature is down to less than 80 DEG C, and vinylite is dissolved in into dilution Agent.
Resin is prepared in proportion, wherein 50 parts of the vinylite containing imine group；15 parts of benzoyl peroxide；Diformazan 10 parts of base aniline；2.5 parts of BYK-A515 defoamers；20 parts of styrene.
The vinylite moulding material of preparation has the characteristics that acid resistance is good, heat-resist and excellent in mechanical performance.Through Test is crossed, moulding material bending strength is 148MPa, tensile strength 98MPa, compressive strength 135MPa, and heat distortion temperature is 125 DEG C, and cure shrinkage is 6.9%.
The vinylite moulding material that above-described embodiment obtains has the technique effect shown in following table after tested：
Test event Unit Example 1 Example 2 Example 3 Example 4 Detection method
Bending strength MPa 145 148 150 148 GB/T 2567-2008
Bending modulus GPa 3.5 3.4 3.5 3.5 GB/T 2567-2008
Tensile strength MPa 96 95 98 98 GB/T 2567-2008
Stretch modulus GPa 3.7 3.6 3.7 3.6 GB/T 2567-2008
Compressive strength MPa 135 138 135 135 GB/T 2567-2008
Modulus of compressibility GPa 3.5 3.4 3.5 3.4 GB/T 2567-2008
Heat distortion temperature ℃ 135 127 130 125 GB/T 1634.3-2004
Cure shrinkage % 6.7 4.7 4.5 6.9 GB/T 24148.9-2014
Acid resistance % 0.0694 0.0563 0.0644 0.0687 GJB 5270-2003
The above-described embodiments merely illustrate the principles and effects of the present invention, and the embodiment that part uses, for For one of ordinary skill in the art, without departing from the concept of the premise of the invention, can also make it is some deformation and Improve, these belong to protection scope of the present invention.

Claims (4)

  1. A kind of 1. large-scale Plumbic acid accumulator container vinylite, it is characterised in that：The raw material structure matched by following parts by weight Into
    50 parts of vinylite
    5-15 parts of curing agent
    2.5-10 parts of accelerator
    2.5 parts of defoamer
    15-20 parts of diluent
    Described curing agent is methyl ethyl ketone peroxide or cyclohexanone peroxide or benzoyl peroxide；Described accelerator is cycloalkanes Sour cobalt or cobalt iso-octoate or dimethylaniline；Described defoamer is BYK-A515；Described diluent is styrene or benzene second Alkene-vinyltoluene mixture；
    Described vinylite contains imine group, is prepared according to following method：
    a）, using THPA and monoethanolamine as raw material, it is reacted first be made imidohydrine；
    b）, using maleic anhydride and imidohydrine as raw material, reacted obtained maleic acid imines ester；
    c）, using maleic acid imines ester and bisphenol A type epoxy resin as raw material, it is reacted be made the vinyl with imine group Resin.
  2. A kind of 2. preparation method of large-scale Plumbic acid accumulator container vinylite as claimed in claim 1, it is characterised in that： Comprise the following steps
    a）, using THPA and monoethanolamine as raw material, it is reacted first be made imidohydrine, wherein THPA and monoethanolamine dosage Mol ratio is 1:1, reaction temperature is 80-100 DEG C, N2Protection, reaction time are 8 hours；
    b）, using maleic anhydride and imidohydrine as raw material, reacted obtained maleic acid imines ester；
    c）, using maleic acid imines ester and bisphenol A type epoxy resin as raw material, it is reacted be made the vinyl with imine group Resin.
  3. 3. a kind of preparation method of large-scale Plumbic acid accumulator container vinylite according to claim 2, its feature exist In described step b）In maleic anhydride and imidohydrine dosage mol ratio be 1:1, sulphuric acid catalysis, reaction temperature For 60 DEG C, the reaction time is 4 hours.
  4. 4. a kind of preparation method of large-scale Plumbic acid accumulator container vinylite according to claim 2, its feature exist In described step c）In maleic acid imines ester and bisphenol A type epoxy resin dosage mol ratio be 2:1, reaction temperature Spend for 120-140 DEG C, catalyst used is catalyst used by epoxy ring-opening esterification, and polymerization inhibitor used is to prevent Polymerization inhibitor used by free yl polymerizating monomer polymerize, reaction time are 4-6 hours, treat that temperature is down to less than 80 DEG C, by ethene Base resin is dissolved in diluent.
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CN105716376B (en) * 2016-01-29 2018-11-02 山东高信化学股份有限公司 A kind of high chlorinated polyethylene drying bed

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CN102838847A (en) * 2012-09-26 2012-12-26 上纬（上海）精细化工有限公司 Composition for improving insulating property of glass reinforced plastic battery jar body
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