CN104031367A - Vacuum infusion resin, preparation method and application thereof - Google Patents
Vacuum infusion resin, preparation method and application thereof Download PDFInfo
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- CN104031367A CN104031367A CN201410240501.7A CN201410240501A CN104031367A CN 104031367 A CN104031367 A CN 104031367A CN 201410240501 A CN201410240501 A CN 201410240501A CN 104031367 A CN104031367 A CN 104031367A
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Abstract
The invention relates to vacuum infusion resin, a preparation method and an application thereof. The resin comprises the following components in parts by weight: 20-50 parts of unsaturated polyester resin a, 20-50 parts of unsaturated monomer b, 0-50 parts of inert filler c, 0.1-1 part of accelerant d, 0.01-0.5 part of polymerization inhibitor e and 1-10 parts of shrinkage reducing component f. The unsaturated polyester resin mixture prepared by the method is very low in viscosity, mild to solidify, and applicable to a vacuum infusion process. Meanwhile, the shrinkage reducing component is added, and linear shrinkage of a resin casting body is smaller than 0.3%, so that the prepared fiber reinforce plastic (FRP) product can be close to zero shrinkage when being solidified at normal temperature, is good in surface condition, and can be up to the A-level surface.
Description
Technical field
The present invention relates to a kind of unsaturated polyester resin compound, particularly a kind of vacuum imports resin combination, preparation method and application thereof.
Background technology
In recent years, along with the progress of industrial technology, more and more higher to the performance requriements of novel material.Glass-reinforced plastic material is due to its superior performance, and development rapidly.But traditional hand paste explained hereafter efficiency is low, vinylbenzene volatilization is large, is in recent years progressively replaced by vacuum introducing technology.It is high that conventional vacuum imports resin viscosity, and curing exotherm is concentrated, and shrinks greatly, causes production efficiency and quality of item to decline, and product surface situation is poor.
Summary of the invention
The object of the invention is to solve above-mentioned deficiency, a kind of unsaturated polyester resin of the DCPD of employing modification is provided, be applicable to vacuum introducing technology, ambient cure, the vacuum that shrinking percentage is zero imports resin, preparation method and application thereof.
The technical scheme that realizes the object of the invention is: a kind of vacuum imports resin, comprise following component, and each constituent mass per-cent is:
20～50 parts of a unsaturated polyester resins, preferably arbitrary integer umber between 20～50;
20～50 parts of b unsaturated monomers, preferably arbitrary integer umber between 20～50;
0～50 part of c inert filler, preferably 1～50 arbitrary integer umber;
0.1～0.5 part of d promotor, preferably 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part;
0.01～0.5 part of e stopper, preferably 0.01 part, 0.02 part, 0.03 part, 0.04 part, 0.05 part, 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part;
F reduces 1～10 part of shrinkage component, preferably 1～10 arbitrary integer umber;
Described unsaturated polyester resin a weight-average molecular weight is 500～10000, in raw materials, Tetra hydro Phthalic anhydride molar content accounts for 0～70% of diprotic acid integral molar quantity, preferably any one integer per-cent between 0～70, MALEIC ANHYDRIDE molar content accounts for the 30-100% of diprotic acid integral molar quantity, any one integer per-cent between can making 30～100, dicyclopentadiene (DCPD) accounts for the 10%-50% of raw material integral molar quantity, preferably any one integer per-cent between 10～50;
Described minimizing shrinkage component f is one or more in polyvinyl acetate (PVAc), polymethylmethacrylate (PMMA), polystyrene (PS);
Described promotor d be in cobalt iso-octoate, cobalt naphthenate, sylvite, calcium salt, vanadic salts, manganese salt, mantoquita, xylidine, Diethyl Aniline, dimethyl-p-toluidine one or more;
Described stopper e be in Resorcinol, para benzoquinone, methyl hydroquinone, p-ten.-butylcatechol one or more.
Contriver is through constantly debugging, countless test adjustment, find that this vacuum imports the preferred each component per-cent of resin and is: 30～40 parts of a unsaturated polyester resins, 30～40 parts of b unsaturated monomers, 15～30 parts of c inert fillers, 0.1～1 part of d promotor, 0.01～0.1 part of e stopper, f reduces 5～10 parts of shrinkage component;
Above-mentioned vacuum imports resin, and more preferably the parts by weight of each component are:
Under this formula, resin viscosity is extremely low, solidifies gently, and the most applicable vacuum introducing technology, and linear shrinkage test is less than 0.3%, close to zero.
Above-mentioned vacuum imports resin, and preferred described minimizing shrinkage component is PVAc, and weight-average molecular weight is 30000～400000
Above-mentioned vacuum imports resin, and preferred described minimizing shrinkage component is saturated polyester, and weight-average molecular weight is 10000～100000
Above-mentioned vacuum imports resin, preferred described unsaturated monomer be in vinylbenzene, methyl methacrylate, methyl acrylate, butyl methacrylate one or more.
Above-mentioned vacuum imports resin, and preferred described unsaturated monomer is vinylbenzene.
The preparation method that above-mentioned vacuum imports resin, first mixes 40%～100wt% of component a, components b total amount; Adopt the components b dissolved constituent f of 1～10wt%; Again the remainder in components b, amount of component b, component d, component e, the component f that dissolved are mixed.
Above-mentioned vacuum imports the application of resin, and it can be by adding ambient cure agent methylethyl ketone peroxide or diacetone peroxide, solidifies at normal temperatures and makes FRP mould.
Saturated polyester of the present invention is the described saturated polyester of patent of invention " mold pressing sheet or Bulk Molding Compound shrinking agent saturated polyester and preparation method thereof " that the applicant applies for and authorizes.
The present invention has positive effect: unsaturated polyester resin mixtures viscosity pole prepared by (1) the present invention is low, solidifies gently, is applicable to vacuum introducing technology; (2) unsaturated polyester resin mixtures that prepared by the present invention, linear shrinkage test is less than 0.3%, far below the 1.5%-2.5% of common unsaturated polyester resin, can think zero contraction, due to the extremely low contraction of resin itself, the FRP goods that make are not seen glass lines substantially, reach A level surface.
Embodiment
(embodiment 1)
One, take unsaturated polyester resin 35g, vinylbenzene 35g, inert filler: aluminium hydroxide 20g, promotor: cobalt octoate 0.3g, stopper: Resorcinol 0.1g, saturated polyester 10g;
Two, prepare unsaturated polyester ester composition
Be first 14g by the 40wt% of component unsaturated polyester resin, vinylbenzene total amount, then dissolve saturated polyester with 3.5g vinylbenzene, more remaining component vinylbenzene, aluminium hydroxide, cobalt octoate, Resorcinol, saturated polyester that dissolving is good are mixed and made.
(embodiment 2)
One, take unsaturated polyester resin 30g, methyl methacrylate 30g, inert filler: aluminium hydroxide 30g, promotor: cobalt naphthenate 0.1g, stopper: para benzoquinone 0.05g, polyvinyl acetate 10g;
Two, prepare unsaturated polyester ester composition
Be first 12g by the 40wt% of component unsaturated polyester resin, methyl methacrylate total amount, be that 2.4g methyl methacrylate dissolves polyvinyl acetate with 8wt% again, more remaining component methyl methacrylate, aluminium hydroxide, cobalt naphthenate, para benzoquinone, polyvinyl acetate that dissolving is good are mixed and made.
(embodiment 3)
One, take unsaturated polyester resin 40g, methyl acrylate 40g, inert filler: aluminium hydroxide 15g, promotor: xylidine 0.4g, stopper: methyl hydroquinone 0.2g, polymethylmethacrylate 5g;
Two, prepare unsaturated polyester ester composition
Be first 16g by the 40wt% of component unsaturated polyester resin, methyl acrylate total amount, dissolve polymethylmethacrylate with 6wt%2.4g methyl acrylate again, more remaining component methyl acrylate, aluminium hydroxide, xylidine, methyl hydroquinone, polymethylmethacrylate that dissolving is good are mixed and made.
(embodiment 4)
One, take unsaturated polyester resin 45g, vinylbenzene 25g, butyl methacrylate 20g, promotor: cobalt octoate 0.3g, stopper: Resorcinol 0.1g, saturated polyester 10g;
Two, prepare unsaturated polyester ester composition
Be first 18g by the 40wt% of component unsaturated polyester resin, vinylbenzene and butyl methacrylate total amount, dissolve saturated polyester with the mixture of 4.5g vinylbenzene and butyl methacrylate again, more remaining component vinylbenzene, butyl methacrylate, aluminium hydroxide, cobalt octoate, Resorcinol, saturated polyester that dissolving is good are mixed and made.
(embodiment 5)
One, take unsaturated polyester resin 50g, vinylbenzene 30g, inert filler: aluminium hydroxide 10g, promotor: cobalt octoate 0.3g, dimethyl-p-toluidine 0.1g, stopper: Resorcinol 0.1g, saturated polyester 10g;
Two, prepare unsaturated polyester ester composition
Be first 12g by the 40wt% of component unsaturated polyester resin, vinylbenzene total amount, be that 1.5g vinylbenzene dissolves saturated polyester with 5wt% again, more remaining component vinylbenzene, aluminium hydroxide, cobalt octoate, dimethyl-p-toluidine, Resorcinol, saturated polyester that dissolving is good are mixed and made.
(embodiment 6)
One, take unsaturated polyester resin 25g, vinylbenzene 25g, inert filler: aluminium hydroxide 45g, promotor: cobalt octoate 0.3g, stopper: Resorcinol 0.1g, saturated polyester 5g;
Two, prepare unsaturated polyester ester composition
Be first 10g by the 40wt% of component unsaturated polyester resin, vinylbenzene total amount, 10wt% dissolves saturated polyester with 2.5g vinylbenzene again, more remaining component vinylbenzene, aluminium hydroxide, cobalt octoate, Resorcinol, saturated polyester that dissolving is good are mixed and made.
(1) the final voltinism data of embodiment 1～6 product are as follows:
When test gel time: solidifying agent uses AKZO M-50, and consumption is 2%.
When testing wire shrinking percentage: 25 DEG C of normal temperature, solidifying agent uses AKZO M-50, and consumption is 2%
(2) the short felt of cutting strengthens physical data:
| Project | Unit | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Testing method |
| Tensile strength | MPa | 100 | 110 | 105 | 108 | 114 | 112 | GB/T1447 |
| Tension set | ％ | 1.8 | 1.5 | 1.6 | 1.3 | 1.9 | 2.1 | GB/T1447 |
| Flexural strength | MPa | 150 | 162 | 154 | 157 | 163 | 168 | GB/T1449 |
| Ba Ke hardness | -- | 55 | 57 | 56 | 53 | 60 | 59 | GB/T3854 |
| Glass fiber content | ％ | 25 | 26 | 31 | 27 | 23 | 29 | GB/T2577 |
Condition of cure: 2%M-50, self-vulcanizing 24 hours, 60 degree are lower to be solidified 3 hours, and 100 degree are lower to be solidified 2 hours.
Above-described specific embodiment; object of the present invention, technical scheme and beneficial effect are further described; institute is understood that; the foregoing is only specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any amendment of making, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (8)
1. vacuum imports a resin, it is characterized in that: comprise following component, and each constituent mass umber:
Described unsaturated polyester resin a weight-average molecular weight is 500～10000, in raw materials, Tetra hydro Phthalic anhydride molar content accounts for 0～70% of diprotic acid integral molar quantity, MALEIC ANHYDRIDE molar content accounts for the 30-100% of diprotic acid integral molar quantity, and dicyclopentadiene accounts for the 10%-50% of raw material integral molar quantity;
Described minimizing shrinkage component f is one or more in saturated polyester, polyvinyl acetate, polymethylmethacrylate, polystyrene.
2. vacuum according to claim 1 imports resin, it is characterized in that: the parts by weight of each component are:
3. vacuum according to claim 1 and 2 imports resin, it is characterized in that: described promotor d be in cobalt iso-octoate, cobalt naphthenate, sylvite, calcium salt, vanadic salts, manganese salt, mantoquita, xylidine, Diethyl Aniline, dimethyl-p-toluidine one or more.
4. vacuum according to claim 1 and 2 imports resin, it is characterized in that: described stopper e be in Resorcinol, para benzoquinone, methyl hydroquinone, p-ten.-butylcatechol one or more.
5. vacuum according to claim 1 and 2 imports resin, it is characterized in that: described unsaturated monomer be in vinylbenzene, methyl methacrylate, methyl acrylate, butyl methacrylate one or more.
6. vacuum according to claim 1 and 2 imports resin, it is characterized in that: described unsaturated monomer is vinylbenzene.
7. the vacuum as described in as arbitrary in claim 1～6 imports a preparation method for resin, it is characterized in that: comprise the steps: that (1) first mix 40～100wt% of component a, components b total amount; (2) get the components b dissolved constituent f of 1～10wt%; (3) the component the f again remainder in components b, amount of component b, component d, component e, step (2) having been dissolved mixes.
8. the vacuum as described in as arbitrary in claim 1～6 imports the application of resin, it is characterized in that: it is applied to vacuum introducing technology and prepares FRP goods, concrete Tong Guo interpolation ambient cure agent methylethyl ketone peroxide or diacetone peroxide, adopt vacuum introducing technology, solidify at normal temperatures and be made into FRP goods.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410240501.7A CN104031367A (en) | 2014-05-30 | 2014-05-30 | Vacuum infusion resin, preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410240501.7A CN104031367A (en) | 2014-05-30 | 2014-05-30 | Vacuum infusion resin, preparation method and application thereof |
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| CN104031367A true CN104031367A (en) | 2014-09-10 |
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| CN201410240501.7A Pending CN104031367A (en) | 2014-05-30 | 2014-05-30 | Vacuum infusion resin, preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669920A (en) * | 2016-03-31 | 2016-06-15 | 武汉理工大学 | Low-shrinkage unsaturated polyester resin and fiber-glass-reinforced board prepared from resin |
| CN106749947A (en) * | 2016-12-03 | 2017-05-31 | 安徽富丽华化工有限公司 | A kind of resistant to elevated temperatures modified unsaturated polyester resin of high tenacity and preparation method thereof |
| CN106832721A (en) * | 2017-03-31 | 2017-06-13 | 张家港九力新材料科技有限公司 | The automobile-used resin of low toxicity high fire-retardance lower shrinkage and its manufacture method |
| CN107603095A (en) * | 2017-09-18 | 2018-01-19 | 张家港九力新材料科技有限公司 | It is a kind of can the shrinking agent that uses of normal temperature and preparation method thereof |
| CN111925637A (en) * | 2020-07-31 | 2020-11-13 | 广东百汇达新材料有限公司 | Rapid curing unsaturated polyester resin for vacuum infusion |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006036839A (en) * | 2004-07-23 | 2006-02-09 | Japan Composite Co Ltd | Unsaturated polyester resin composition, molding material and molding comprising the same |
| CN102206310A (en) * | 2011-04-22 | 2011-10-05 | 常州华科树脂有限公司 | Vacuum lead-in unsaturated polyester resin for fan blade and preparation method thereof |
-
2014
- 2014-05-30 CN CN201410240501.7A patent/CN104031367A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006036839A (en) * | 2004-07-23 | 2006-02-09 | Japan Composite Co Ltd | Unsaturated polyester resin composition, molding material and molding comprising the same |
| CN102206310A (en) * | 2011-04-22 | 2011-10-05 | 常州华科树脂有限公司 | Vacuum lead-in unsaturated polyester resin for fan blade and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669920A (en) * | 2016-03-31 | 2016-06-15 | 武汉理工大学 | Low-shrinkage unsaturated polyester resin and fiber-glass-reinforced board prepared from resin |
| CN105669920B (en) * | 2016-03-31 | 2018-05-01 | 武汉理工大学 | A kind of low shrinking unsaturated polyester resin and based on the standby glass fiber reinforcement plate of the resin-made |
| CN106749947A (en) * | 2016-12-03 | 2017-05-31 | 安徽富丽华化工有限公司 | A kind of resistant to elevated temperatures modified unsaturated polyester resin of high tenacity and preparation method thereof |
| CN106832721A (en) * | 2017-03-31 | 2017-06-13 | 张家港九力新材料科技有限公司 | The automobile-used resin of low toxicity high fire-retardance lower shrinkage and its manufacture method |
| CN107603095A (en) * | 2017-09-18 | 2018-01-19 | 张家港九力新材料科技有限公司 | It is a kind of can the shrinking agent that uses of normal temperature and preparation method thereof |
| CN111925637A (en) * | 2020-07-31 | 2020-11-13 | 广东百汇达新材料有限公司 | Rapid curing unsaturated polyester resin for vacuum infusion |
| CN111925637B (en) * | 2020-07-31 | 2023-12-05 | 广东百汇达新材料有限公司 | Rapid-curing unsaturated polyester resin for vacuum introduction |
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Application publication date: 20140910 |
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