CN109705259A - A kind of damage resistant, high surface hardness thermoplastic resin, plastics and preparation method - Google Patents
A kind of damage resistant, high surface hardness thermoplastic resin, plastics and preparation method Download PDFInfo
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- CN109705259A CN109705259A CN201811575018.9A CN201811575018A CN109705259A CN 109705259 A CN109705259 A CN 109705259A CN 201811575018 A CN201811575018 A CN 201811575018A CN 109705259 A CN109705259 A CN 109705259A
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Abstract
The present invention relates to resin modified technical field, in particular to a kind of damage resistant, high surface hardness thermoplastic resin, plastics and preparation method.The preparation method of thermoplastic resin includes following preparation step: being successively uniformly mixed the initiator that mass ratio is 78%-92% matrix resin monomer, 2%-15% flexible unit, 2%-15% auxiliary monomer and 0.3%-1%；It is slowly dropped to being under reflux temperature in organic solvent for 1-4 times of equal monomers summation quality, controls feed time in 4-5h；Constant temperature drops to 45 DEG C hereinafter, filtering and obtaining acrylic resin much filtrate to temperature to 70 DEG C or less 2h after reaction；After being washed 4-5 times with clear water, drying obtains acrylic resin solid at 60-70 DEG C.The thermoplastic resin that this law provides can effectively promote the scratch resistant performance and surface hardness of plastics, especially suitable for being with a wide range of applications in one or more of plastics such as ABS, ASA, PC, PMMA, HIPS.
Description
Technical field
The present invention relates to resin modified technical field, in particular to a kind of damage resistant, high surface hardness thermoplastic resin, modeling
Material and preparation method.
Background technique
The generally existing not damage resistant of now widely used plastics, the low disadvantage of surface hardness are generally by coating process
Improved, as the idea of environmental protection and sustainable development gradually allows more people to receive, spraying, electroplating technology have pollution ring
Therefore how border and the low problem of yield rate promote the damage resistant of plastics itself, surface hardness becomes that industry faces newly asks
Topic.
Summary of the invention
To solve the problems in above-mentioned background technique, the present invention provides a kind of damage resistant, high surface hardness thermoplastic propene
Acid resin has a structure that
A (matrix resin monomer)X- B (flexible unit)Y- C (auxiliary monomer)Z；
Wherein, A is methacrylic acid isobornylene or glycidyl methacrylate；
B is flexible unit, including in methyl acrylate, ethyl acrylate, n-octyl, hexyl methacrylate
It is at least one；
C is auxiliary monomer, be acrylonitrile in or propylene oxide；
Wherein, X, Y, Z are greater than 0.
One ground of progress, it is 78%-92% that the A, which accounts for resin ratio,；It is 2%-15% that the B, which accounts for resin ratio,；The C is accounted for
Resin ratio is 2%-15%.
The present invention is using methacrylic acid isobornylene or glycidyl methacrylate as matrix resin monomer, energy
Glass transition temperature Tg is enough improved, and then improves the hardness of material；By selecting the flexible unit of corresponding proportion that can guarantee
Resin has certain flexibility；In addition, the present invention selects in 2%-15% acrylonitrile or propylene oxide is as auxiliary monomer, energy
Carry out methacrylic acid isobornylene or glycidyl methacrylate with flexible unit good compatible, moreover it is possible to improve
The mobility of material entirety prevents manufactured resin material brittleness higher, to improve the applicability of material.
One ground of progress, the number-average molecular weight of the thermoplastic acrylic resins are 20000-80000.
The present invention also provides a kind of basis any damage resistants as above, high surface hardness thermoplastic propene's acids plastics
Preparation method, including following preparation step:
It step a, by mass ratio is successively 78%-92% matrix resin monomer, 2%-15% flexible unit, 2%-15% auxiliary
The initiator of monomer and 0.3%-1% is helped to be uniformly mixed；
Step b, it is slowly dropped to being under reflux temperature in organic solvent for the monomers summation quality such as 1-4 times, control adds
Expect the time in 3-5h；
Step c, constant temperature then is cooled to 45 DEG C hereinafter, filtering and obtaining acrylic acid tree to 70 DEG C or less 2h after reaction
Rouge much filtrate；
Step d, after being washed 4-5 times with clear water, drying obtains acrylic resin solid at 60-70 DEG C.
Progress one ground, the initiator be dibenzoyl peroxide, tert-Butylbenzene formyl, azodiisobutyronitrile,
Dilauroyl peroxide；
Further, the organic solvent is butyl glycol ether/isobutanol (mass ratio 7/3), butyl acetate, toluene；Its
In, butyl glycol ether/isobutanol is preferentially selected, and controlling mass ratio is 7/3, can make the solubility parameter 8- of solvent for use
10.3, guarantee that polymer synthesis process middle-molecular-weihydroxyethyl increases in OK range and can be precipitated in time, can be improved and prepare yield；
The present invention also provides a kind of damage resistants, high surface hardness thermoplastic, using the acrylic acid prepared as described above
The acrylic resin solid is blended with matrix plastic according to the ratio of mass component 10%-40% by double resin solid
Screw extruder melting extrusion is granulated, and obtains damage resistant, high surface hardness thermoplastic.
Further, described matrix plastics include one of ABS, ASA, PC, PMMA or HI PS or a variety of mixing.
Damage resistant provided by the invention, high surface hardness thermoplastic resin pass through the acrylic acid of design linear low molecular weight
Resin is conducive in the process after blending, and the acrylic resin of low molecular weight forms hard table in frosting
Layer improves the plastics not low disadvantage of damage resistant, table hardness.The method that this law provides can effectively promote the scratch resistance of plastics
Can and surface hardness, and can further apply it is a few days ago more popular exempt from painted plastic product, it is synchronous to realize that environmental protection is wanted
The improvement demand of summation plastics damage resistant and surface hardness, it is a kind of or several especially suitable for ABS, ASA, PC, PMMA, H I PS etc.
In kind plastics, it is with a wide range of applications.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In technical solution be clearly and completely described, it is clear that described embodiments are some of the embodiments of the present invention, without
It is whole embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not before making creative work
Every other embodiment obtained is put, shall fall within the protection scope of the present invention.
The present invention also provides embodiments as shown:
Embodiment 1
(1) successively by mass ratio be 85% methacrylic acid isobornylene, 4% acrylonitrile, 4% ethyl acrylate, 6.3%
N-octyl and 0.7% dibenzoyl peroxide are uniformly mixed, and are slowly dropped to being in back for equal monomers summation quality
In butyl glycol ether/isobutanol (mass ratio 7/3) at a temperature of stream, feed time is controlled in 5h；
Constant temperature drops to 45 DEG C hereinafter, filtering and obtaining acrylic resin to temperature to 70 DEG C or less 2h after reaction
Much filtrate；
After being washed 4-5 times with clear water, drying obtains acrylic resin solid at 60-70 DEG C；The equal molecule of gained resin number
Amount is 67000, yield 96%.
(2) (1) resulting acrylic resin solid is blended according to the ratio of component about 15% with ABS and is squeezed by twin-screw
Machine melting extrusion is granulated out, obtains a kind of damage resistant, high surface hardness thermoplastic.
Embodiment 2
(1) successively by mass ratio be 85% methacrylic acid isobornylene, 4% acrylonitrile, 4% ethyl acrylate, 6.3%
N-octyl and 0.7% dibenzoyl peroxide are uniformly mixed, and are slowly dropped to being in back for equal monomers summation quality
In butyl acetate at a temperature of stream, feed time is controlled in 5h；
Constant temperature drops to 45 DEG C hereinafter, filtering and obtaining acrylic resin to temperature to 70 DEG C or less 2h after reaction
Much filtrate；
After being washed 4-5 times with clear water, drying obtains acrylic resin solid at 60-70 DEG C；The equal molecule of gained resin number
Amount is 67000, yield 89%.
(2) (1) resulting acrylic resin solid is blended according to the ratio of component about 15% with ABS and is squeezed by twin-screw
Machine melting extrusion is granulated out, obtains 1 sample of embodiment.
Embodiment 3
It (1) by mass ratio is successively 82% glycidyl methacrylate, 4% acrylonitrile, 4% propylene oxide, 6% the third
Olefin(e) acid n-octyl, 3.5% ethyl acrylate and 0.5% dibenzoyl peroxide are uniformly mixed, and it is total to be slowly dropped to equal monomers
With quality in butyl glycol ether/isobutanol (mass ratio 7/3) under reflux temperature, feed time is controlled in 5h；
Constant temperature drops to 45 DEG C hereinafter, filtering and obtaining acrylic resin to temperature to 70 DEG C or less 2h after reaction
Much filtrate.After being washed 4-5 times with clear water, drying obtains acrylic resin solid at 60-70 DEG C.Gained resin number-average molecular weight
It is 75000, yield 95%.
(2) (1) resulting acrylic resin solid is blended according to the ratio of component about 20% with PC/ABS (7/3) and is passed through
Double screw extruder melting extrusion is granulated, and obtains 2 sample of embodiment.
Comparative example 1
90% Isobutyl methacrylate, 9.5% acrylonitrile are uniformly mixed according to 0.5% dibenzoyl peroxide,
It is slowly dropped to being in butyl glycol ether/isobutanol (mass ratio 7/3) under reflux temperature for equal monomers summation quality, control
Feed time is in 5h；
Constant temperature drops to 45 DEG C hereinafter, filtering and obtaining acrylic resin to temperature to 70 DEG C or less 2h after reaction
Much filtrate.After being washed 4-5 times with clear water, drying obtains acrylic resin solid at 60-70 DEG C.Gained resin number-average molecular weight
It is 75000, yield 86%.
(2) (1) resulting acrylic resin solid is blended according to the ratio of component about 20% with PC/ABS (7/3) and is passed through
Double screw extruder melting extrusion is granulated, and obtains 1 sample of comparative example.
Comparative example 2
90% methyl acrylate, 9.5% acrylonitrile are uniformly mixed according to 0.5% dibenzoyl peroxide, slowly dripped
It is added to being in butyl glycol ether/isobutanol (mass ratio 7/3) under reflux temperature for equal monomers summation quality, when control feeds
Between in 5h；
Constant temperature drops to 45 DEG C hereinafter, filtering and obtaining acrylic resin to temperature to 70 DEG C or less 2h after reaction
Much filtrate.After being washed 4-5 times with clear water, drying obtains acrylic resin solid at 60-70 DEG C.Gained resin number-average molecular weight
It is 75000, yield 89%.
(2) (1) resulting acrylic resin solid is blended according to the ratio of component about 20% with PC/ABS (7/3) and is passed through
Double screw extruder melting extrusion is granulated, and obtains 2 sample of comparative example.
By it is above-mentioned be that embodiment and comparative example is tested accordingly, test method (testing standard) are as follows: simply supported beam notch
Impact strength is tested referring to GBT 1043.1-2008, and Rockwell hardness is tested referring to GBT 3398.2-2008, pencil
Hardness is tested referring to GBT 6739-2006, and glossiness test is tested referring to GB 8807-88.
Test result is as follows shown in table:
Table 1
Damage resistant provided by the invention, high surface hardness thermoplastic propene's acids it can be seen from above-mentioned test and result
Resin can be such that the yield of resin greatly improves, in addition, sample surfaces obtained have by selecting specific raw material and proportion
High hardness has good scratch resistant performance, and is still able to maintain 90% or so glossiness.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (8)
1. a kind of damage resistant, high surface hardness thermoplastic resin, which is characterized in that its structural formula is as follows:
A (matrix resin monomer)X- B (flexible unit)Y- C (auxiliary monomer)Z；
Wherein, A is methacrylic acid isobornylene or glycidyl methacrylate；
B is flexible unit, including in methyl acrylate, ethyl acrylate, n-octyl, hexyl methacrylate at least
It is a kind of；
C is auxiliary monomer, be acrylonitrile in or propylene oxide；
Wherein, X, Y, Z are greater than 0.
2. damage resistant according to claim 1, high surface hardness thermoplastic resin, it is characterised in that: the A accounts for resin ratio
Example is 78%-92%；It is 2%-15% that the B, which accounts for resin ratio,；It is 2%-15% that the C, which accounts for resin ratio,.
3. damage resistant according to claim 1, high surface hardness thermoplastic resin, it is characterised in that: the thermoplastic resin
The number-average molecular weight of rouge is 20000-80000.
4. a kind of preparation method according to damage resistant as described in any one of claims 1-3, high surface hardness thermoplastic resin,
It is characterised in that it includes following preparation step:
Step a, successively by mass ratio to be that 78%-92% matrix resin monomer, 2%-15% flexible unit, 2%-15% are assisted single
The initiator of body and 0.3%-1% are uniformly mixed；
Step b, it is added drop-wise to being under reflux temperature in organic solvent for the monomers summation quality such as 1-4 times, control feed time exists
3-5h；
Step c, constant temperature drops to 45 DEG C hereinafter, filtering and obtaining acrylic acid tree to temperature to 70 DEG C or less 2h after reaction
Rouge much filtrate；
Step d, after being washed 4-5 times with clear water, drying obtains the resin at 60-70 DEG C.
5. the preparation method of damage resistant according to claim 4, high surface hardness thermoplastic resin, it is characterised in that: institute
Stating initiator is in dibenzoyl peroxide, tert-Butylbenzene formyl, azodiisobutyronitrile or dilauroyl peroxide
At least one.
6. the preparation method of damage resistant according to claim 4, high surface hardness thermoplastic resin, it is characterised in that: step
In rapid b, the organic solvent be in butyl glycol ether/isobutanol, butyl acetate or toluene wherein；Wherein, the ethylene glycol
The ratio of butyl ether and isobutanol is 7:3.
7. the preparation method of a kind of damage resistant, high surface hardness thermoplastic, it is characterised in that: using such as claim 4 institute
The acrylic resin solid for stating preparation, by the acrylic resin solid according to the ratio and matrix of mass component 10%-40%
Plastic blend is granulated by double screw extruder melting extrusion, obtains damage resistant, high surface hardness thermoplastic.
8. the preparation method of damage resistant according to claim 7, high surface hardness thermoplastic, it is characterised in that: institute
Stating matrix plastic includes one of ABS, ASA, PC, PMMA or HIPS or a variety of mixing.
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| CN201811575018.9A CN109705259B (en) | 2018-12-21 | 2018-12-21 | Scratch-resistant high-surface-hardness thermoplastic resin, plastic and preparation method |
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| CN201811575018.9A CN109705259B (en) | 2018-12-21 | 2018-12-21 | Scratch-resistant high-surface-hardness thermoplastic resin, plastic and preparation method |
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| CN109705259A true CN109705259A (en) | 2019-05-03 |
| CN109705259B CN109705259B (en) | 2020-12-11 |
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Citations (6)
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|---|---|---|---|---|
| JPH0649292A (en) * | 1992-08-03 | 1994-02-22 | Sumitomo Bakelite Co Ltd | Thermoplastic resin composition |
| CN101200583A (en) * | 2006-12-13 | 2008-06-18 | 第一毛织株式会社 | Scratch-resistant flame retardant thermoplastic resin composition |
| CN102007183A (en) * | 2008-04-14 | 2011-04-06 | 第一毛织株式会社 | Flame-retardant scratch-resistant thermoplastic resin composition with improved compatibility |
| CN102690385A (en) * | 2012-06-01 | 2012-09-26 | 安徽省金盾涂料有限责任公司 | Method for polymerizing water-borne acrylate coating |
| CN103130944A (en) * | 2013-02-21 | 2013-06-05 | 西安交通大学 | Preparation method of high-reaction-activity hydroxyl acrylic resin |
| CN107793982A (en) * | 2017-10-26 | 2018-03-13 | 鹤山市怡信化工厂有限公司 | A kind of new Epoxy-imide adhesive and preparation method |
-
2018
- 2018-12-21 CN CN201811575018.9A patent/CN109705259B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0649292A (en) * | 1992-08-03 | 1994-02-22 | Sumitomo Bakelite Co Ltd | Thermoplastic resin composition |
| CN101200583A (en) * | 2006-12-13 | 2008-06-18 | 第一毛织株式会社 | Scratch-resistant flame retardant thermoplastic resin composition |
| CN102007183A (en) * | 2008-04-14 | 2011-04-06 | 第一毛织株式会社 | Flame-retardant scratch-resistant thermoplastic resin composition with improved compatibility |
| CN102690385A (en) * | 2012-06-01 | 2012-09-26 | 安徽省金盾涂料有限责任公司 | Method for polymerizing water-borne acrylate coating |
| CN103130944A (en) * | 2013-02-21 | 2013-06-05 | 西安交通大学 | Preparation method of high-reaction-activity hydroxyl acrylic resin |
| CN107793982A (en) * | 2017-10-26 | 2018-03-13 | 鹤山市怡信化工厂有限公司 | A kind of new Epoxy-imide adhesive and preparation method |
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