CN102199332B - Method for preparing chemical compound type macromolecular toughening brightening additive used for plastics and product thereof - Google Patents
Method for preparing chemical compound type macromolecular toughening brightening additive used for plastics and product thereof Download PDFInfo
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- CN102199332B CN102199332B CN 201110087483 CN201110087483A CN102199332B CN 102199332 B CN102199332 B CN 102199332B CN 201110087483 CN201110087483 CN 201110087483 CN 201110087483 A CN201110087483 A CN 201110087483A CN 102199332 B CN102199332 B CN 102199332B
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Abstract
The invention relates to a method for preparing a chemical compound type macromolecular toughening brightening additive used for plastics and a product thereof. The method comprises: sprinkling a coupling agent with a mass fraction of 0.5% to 8% of that of an inorganic brightening agent into 20 to 60 parts of stirring inorganic brightening agent powder, keeping for a certain period of time, obtaining the inorganic brightening agent anchored to the coupling agent; mixing the inorganic brightening agent anchored to the coupling agent with 20 to 80 parts of thermoplastic elastomer, 0.5 to 5 parts of polymer fluorescent brightening agent, 0.2 to 1.0 parts of peroxide initiator, 0.1 to 0.2 parts of anti-oxidant and 0.3 to 1.5 parts of lubricant in a high stirring machine, adding the obtained mixture into a mixing type double screw extruder, obtaining the macromolecular toughening brightening additive through the working procedures of mixing, extruding, grinding and cooling. The additive provided in the invention is the chemical compound type macromolecular toughening brightening additive used for plastics, which ingrates the functions of toughening, brightening and environmental protecting.
Description
Technical field
The present invention relates to a kind of macromolecular toughening whitening agent and preparation method thereof, belong to the additive that modifying plastics is used, particularly a kind of plastics brighten the preparation method of additive with chemically composited type macromolecular toughening.
Background technology
A lot of plastics require that work in-process brightens, the plastics of blast, toughness reinforcing, particularly some recycles, need modification, to obtain good appearance and mechanical property.The method that now adopts is: brighten and add the inorganic brighteners powder; Blast, brighten, add white dyes; Toughness reinforcing interpolation rubber elastomer composition.They and mixed with resin are processed.There is following shortcoming in such conventional approach: (1) their blending dispersion is difficult to evenly, and the toughness reinforcing effect of blast is brightened in impact; (2) white dyes is small molecules, be easy to move, ooze out, run off, and scrubbing resistance not, light fugitive is shone and long term thermal temperature environment, and whiteness easily descends, and gloss is easily lost.(3) inorganic brighteners powder and many resin compatibles are bad, Mechanical Properties of Products is descended, and be easy to separate out efflorescence; (4) when being processed into goods, powder pollutes production environment.
Summary of the invention
For solving the problems of the technologies described above, the present invention adopts chemically composited method, the links such as superpolymer elastomer, inorganic brighteners, macromolecular elastic fluorescent brightening agent are got up, become object of the present invention, prepare and a kind ofly integrate toughness reinforcing, brighten, the functional plastic of blast, environmental protection brightens addictive preparation method and goods with chemically composited type macromolecular toughening.
Plastics brighten addictive preparation method with chemically composited type macromolecular toughening to carry out as follows:
1) will be that 0.5～8% coupling agent of inorganic brighteners is sprayed on 20～60 parts in the stirring by massfraction,
In the inorganic brighteners powder, stir maintenance 5～30 minutes, below the temperature 50 C.Become anchoring and the inorganic brighteners of coupling agent;
2), with step 1) system the inorganic brighteners of anchoring coupling agent stir in the machine at height and mix with 20～80 parts of thermoplastic elastomers, 0.5～5 part of macromolecular elastic fluorescent brightening agent, 0.2～1.0 part of peroxide initiator, 0.1～0.2 part of oxidation inhibitor, 0.3～1.5 part of lubricant, churning time 5～20 minutes, temperature is controlled at below 50 ℃.
3), with step 2) system mixture add the mixed milling type twin screw extruder, through macromolecular toughening whitening agent mixing, that extrude, make after the pelletizing, cooling.Temperature control is 150～200 ℃ in the mixed milling type twin screw extruder, 150～400 rev/mins of screw speeds.
The described inorganic brighteners of step 1) is titanium dioxide, lithopone, barium sulfate base TiO
2Composite white pigment, TiO
2A kind of in the coating calcium carbonate white pigment etc.
The described coupling agent of step 1) is vinyltriethoxysilane, azido-Trimethoxy silane.
Step 2) described thermal plastic high polymer elastomerics is a kind of among SBS, SEBS, EPEM, the EPR.
Step 2) described macromolecule fluorescence whitener is a kind of grafting body among triazine amino-stilbene type white dyes monomer and SBS, SEBS, EPDM, the EPR.
Its structural formula is:
In prescription, the superpolymer in thermoplastic elastomer and the macromolecular elastic fluorescent brightening agent must be identical.
The macromolecular toughening that the present invention makes brightens additive, it is characterized in that superpolymer elastomer, inorganic brighteners link by chemical reaction with macromolecular elastic fluorescent brightening agent, become object of the present invention.
Matrix resin of the present invention is thermoplastic elastomer, contains certain two keys, and inorganic brighteners is the inorganic powder of strong covering power.Chemical bonding between them reaches by coupling agent.Employed coupling agent contains two keys or azido group, and it can be on the one hand and the inorganic securely Chemical bond of powder that brightens, and is under the initiator effect, crosslinked with double bond containing thermoplastic elastomer on the other hand.
The macromolecular elastic fluorescent brightening agent that adopts is the grafts of white dyes monomer on elastopolymer, the Polymers Phase of using on its elastopolymer part and the above-mentioned inorganic brighteners with, good consistency is arranged, and under initiator and shear action, also there is bonding reaction to occur with double bond containing coupling agent.With them by a certain percentage, make object of the present invention by mixing reaction.
With system macromolecular toughening brighten additive and in the plastics such as PP, PE, PVC, PC alloy, use respectively, particularly in the modification of relevant reclaimed materials, use, carry out toughness reinforcing, brighten, the blast modification.Result of use is compared with the traditional product that adds same amount, brightens brightening effect and obviously improves, and the mechanical properties such as toughness reinforcing, anti-impact are obviously improved.Particularly shone 40 days under the sunlight, additive of the present invention is without oozing out, and without powder phenomenon-tion, whiteness reduces seldom; And the goods that traditional product is added have powder phenomenon-tion, and relatively add the whiteness of properties-correcting agent of the present invention, traditional product to hang down 15～18%.This is the result of high molecular of properties-correcting agent of the present invention, and properties-correcting agent of the present invention has the feature of environmental protection simultaneously.
Embodiment
The present invention is described further below in conjunction with specific embodiment.
Embodiment 1:
1) will be that 0.25 part vinyltriethoxysilane coupling agent is sprayed in 20 parts of titanium dioxide powders in the stirring with the dilution of the methyl alcohol of 1:1 by massfraction,, kept 5～30 minutes, the control temperature is below 50 ℃, and making becomes the inorganic brighteners that coupling agent in anchoring;
2), with step 1) the titanium dioxide whitening agent of anchoring coupling agent of system stirs at height with 40 thermoplastic elastomer SBSs, 0.8 part of SBS macromolecule fluorescence whitener, 0.2 part of dicumyl peroxide, 0.1 part of oxidation inhibitor B215,0.3 part of paraffin oil lubricant etc. and mixes in the machine, churning time 5～10 minutes is below the temperature 50 C.
3), with step 2) system mixture add in the hopper of mixed milling type twin screw extruder, when dual-screw-stem machine is heated to 150～200 ℃, start charging machine and dual-screw-stem machine, material evenly enter carry out in the dual-screw-stem machine mixing, plastify, extrude, make the macromolecular toughening whitening agent after the pelletizing, cooling.Mixing, plastify, extrude 150～200 ℃ of middle temperature controls, 150～400 rev/mins of screw speeds.
Embodiment 2:
1) will be that 0.50 part azido-Trimethoxy silane (with methyl alcohol equal in quality dilution) coupling agent is sprayed on 60 parts of barium sulfate base TiO in the stirring by massfraction,
2Composite white pigment kept 5～30 minutes, and temperature becomes the inorganic brighteners that coupling agent in anchoring below 50 ℃;
2), with step 1) inorganic brighteners of the anchoring coupling agent that makes stirs in the machine at height and mixes with 40 parts of thermoplastic elastomer EPDM, 3 parts of EPDM macromolecule fluorescence whiteners, 0.5 part of di-t-butyl peroxide initiator, 0.2 part of oxidation inhibitor B215,0.8 part of polyethylene wax, mixing time 5～15 minutes, 400 rev/mins of rotating speeds, temperature are no more than 50 ℃.
3), with step 2) mixture that makes adds in the hopper of mixed milling type twin screw extruder, the preheating twin screw extruder makes it reach 150～200 ℃, starts charging machine and dual-screw-stem machine, material evenly enters in the dual-screw-stem machine, carry out mixing, plastify, extrude.And keep 150～200 ℃ of temperature, 200～400 rev/mins of screw speeds.The material of extruding obtains polymer and brightens toughness reinforcing pellet through fervent, air-cooled.
Additive of the present invention, is applied to plastics PP(and contains partially recycled material in the situation that to brighten significant quantity identical with conventional additive) effect be compared as follows:
Can find out by embodiment, the present invention relates to a kind of plastics and brighten addictive preparation method and goods with chemically composited type macromolecular toughening,
The preparation method carries out as follows:
1) will be that 0.5～8% coupling agent of inorganic brighteners is sprayed on 20～60 parts in the stirring by massfraction,
In the inorganic brighteners powder, stir maintenance 5～30 minutes, below the temperature 50 C.Become anchoring and the inorganic brighteners of coupling agent;
2), with step 1) inorganic brighteners of anchoring coupling agent of system stirs in the machine at height and mixes with 20～80 parts of thermoplastic elastomers, 0.5～5 part of macromolecular elastic fluorescent brightening agent, 0.2～1.0 part of peroxide initiator, 0.1～0.2 part of oxidation inhibitor, 0.3～1.5 part of lubricant, churning time 5～20 minutes, temperature is controlled at below 50 ℃.
3), with step 2) system mixture add the mixed milling type twin screw extruder, through macromolecular toughening whitening agent mixing, that extrude, make after the pelletizing, cooling.Temperature control is 150～200 ℃ in the mixed milling type twin screw extruder, 150～400 rev/mins of screw speeds.
The described inorganic brighteners of step 1) is titanium dioxide, lithopone, barium sulfate base TiO
2Composite white pigment, TiO
2A kind of in the coating calcium carbonate white pigment etc.
The described coupling agent of step 1) is vinyltriethoxysilane, azido-Trimethoxy silane.
Step 2) described thermal plastic high polymer elastomerics is a kind of among SBS, SEBS, EPEM, the EPR.
Step 2) described macromolecule fluorescence whitener is a kind of grafting body among triazine amino-stilbene type white dyes monomer and SBS, SEBS, EPDM, the EPR.
Its structural formula is:
In prescription, the superpolymer in thermoplastic elastomer and the macromolecular elastic fluorescent brightening agent must be identical.
The macromolecular toughening that the present invention makes brightens additive, it is characterized in that superpolymer elastomer, inorganic brighteners link by chemical reaction with macromolecular elastic fluorescent brightening agent, become object of the present invention.
Matrix resin of the present invention is thermoplastic elastomer, contains certain two keys, and inorganic brighteners is the inorganic powder of strong covering power.Chemical bonding between them reaches by coupling agent.Employed coupling agent contains two keys or azido group, and it can be on the one hand and the inorganic securely Chemical bond of powder that brightens, and is under the initiator effect, crosslinked with double bond containing thermoplastic elastomer on the other hand.
The macromolecular elastic fluorescent brightening agent that adopts is the grafts of white dyes monomer on elastopolymer, the Polymers Phase of using on its elastopolymer part and the above-mentioned inorganic brighteners with, good consistency is arranged, and under initiator and shear action, also there is bonding reaction to occur with double bond containing coupling agent.With them by a certain percentage, make object of the present invention by mixing reaction.
Claims (6)
1. plastics brighten the preparation method of additive with chemically composited type macromolecular toughening, it is characterized in that carrying out as follows:
1) will be that 0.5～8% coupling agent of inorganic brighteners is sprayed on 20～60 parts in the stirring by massfraction,
In the inorganic brighteners powder, stir maintenance 5～30 minutes, below the temperature 50 C, become the inorganic brighteners that coupling agent in anchoring;
2), with step 1) system the inorganic brighteners of anchoring coupling agent stir in the machine at height and mix with 20～80 parts of thermal plastic high polymer elastomericss, 0.5～5 part of macromolecular elastic fluorescent brightening agent, 0.2～1.0 part of peroxide initiator, 0.1～0.2 part of oxidation inhibitor, 0.3～1.5 part of lubricant, churning time 5～20 minutes, temperature are controlled at below 50 ℃;
3), with step 2) mixture that makes adds the mixed milling type twin screw extruder, through macromolecular toughening whitening agent mixing, that extrude, make after the pelletizing, cooling, temperature control is 150～200 ℃ in the mixed milling type twin screw extruder, 150～400 rev/mins of screw speeds;
Described inorganic brighteners is titanium dioxide, lithopone, barium sulfate base TiO
2Composite white pigment, TiO
2A kind of in the coating calcium carbonate white pigment;
Described thermal plastic high polymer elastomerics is a kind of among SBS, SEBS, EPEM, the EPR; Described coupling agent is a kind of in vinyltriethoxysilane, the azido-Trimethoxy silane; Described oxidation inhibitor is B215; Described lubricant is paraffin oil or polyethylene wax;
Described macromolecular elastic fluorescent brightening agent is a kind of in the grafting body of triazine amino-stilbene type white dyes monomer and SBS, SEBS, EPDM, EPR, and its polymer moiety is identical with the thermal plastic high polymer elastomer portion of adding, and its structural formula is:
2. plastics according to claim 1 brighten the preparation method of additive with chemically composited type macromolecular toughening, it is characterized in that described peroxide initiator is dicumyl peroxide or di-t-butyl peroxide initiator.
3. plastics according to claim 1 brighten the preparation method of additive with chemically composited type macromolecular toughening, it is characterized in that described coupling agent dilutes with the methyl alcohol of 1:1.
4. goods that brighten the preparation method of additive according to the described plastics of claim 1 with chemically composited type macromolecular toughening is characterized in that thermal plastic high polymer elastomerics, inorganic brighteners link with macromolecular elastic fluorescent brightening agent.
5. want 1 described plastics to brighten the preparation method's of additive goods with chemically composited type macromolecular toughening according to right, it is characterized in that matrix resin is thermoplastic elastomer, contain certain two keys, inorganic brighteners is the inorganic powder of strong covering power.
6. plastics according to claim 5 brighten the preparation method's of additive goods with chemically composited type macromolecular toughening, it is characterized in that the macromolecular elastic fluorescent brightening agent that adopts is the grafts of white dyes monomer on elastopolymer, the Polymers Phase of using on its elastopolymer part and the above-mentioned inorganic brighteners with, good consistency is arranged, and under initiator and shear action, also there is bonding reaction to occur with double bond containing coupling agent; Described inorganic brighteners is titanium dioxide, lithopone, barium sulfate base TiO
2Composite white pigment, TiO
2A kind of in the coating calcium carbonate white pigment;
Described thermal plastic high polymer elastomerics is a kind of among SBS, SEBS, EPEM, the EPR; Described coupling agent is a kind of in vinyltriethoxysilane, the azido-Trimethoxy silane; Described oxidation inhibitor is B215; Described lubricant is paraffin oil or polyethylene wax;
Described macromolecular elastic fluorescent brightening agent is a kind of in the grafting body of triazine amino-stilbene type white dyes monomer and SBS, SEBS, EPDM, EPR, and its polymer moiety is identical with the thermal plastic high polymer elastomer portion of adding, and its structural formula is:
。
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201110087483 CN102199332B (en) | 2011-04-08 | 2011-04-08 | Method for preparing chemical compound type macromolecular toughening brightening additive used for plastics and product thereof |
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| CN 201110087483 CN102199332B (en) | 2011-04-08 | 2011-04-08 | Method for preparing chemical compound type macromolecular toughening brightening additive used for plastics and product thereof |
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| CN102199332B true CN102199332B (en) | 2013-02-13 |
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| CN109503890B (en) * | 2018-12-12 | 2021-03-02 | 怀化学院 | Chemical composite whitening agent for polyurethane sponge and preparation method thereof |
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| CN101328697B (en) * | 2007-06-21 | 2010-11-17 | 上海雅运纺织助剂有限公司 | Liquid fluorescent whitening agent mixture preparation |
| JP2009013429A (en) * | 2008-10-22 | 2009-01-22 | Riken Technos Corp | Thermoplastic elastomer composition |
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Effective date of registration: 20170527 Address after: 412005 Hunan Province, Zhuzhou Shifeng District Tianxin high-tech park Burson Road No. 8 Patentee after: Hunan Shengu new materials Co. Ltd. Address before: 412005 Hunan Province, Zhuzhou Shifeng District Tianxin high-tech park Burson Road No. 8 Patentee before: Zhuzhou Jingyu Industrial Co.,Ltd. |
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Granted publication date: 20130213 Termination date: 20210408 |
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