CN101385958A - Polyester type amphipathic nature ultra-dispersant and preparation method thereof - Google Patents
Polyester type amphipathic nature ultra-dispersant and preparation method thereof Download PDFInfo
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- CN101385958A CN101385958A CNA2008102318009A CN200810231800A CN101385958A CN 101385958 A CN101385958 A CN 101385958A CN A2008102318009 A CNA2008102318009 A CN A2008102318009A CN 200810231800 A CN200810231800 A CN 200810231800A CN 101385958 A CN101385958 A CN 101385958A
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Abstract
The invention relates to a polyester amphipathic hyper-dispersant and a preparation method thereof to satisfy the demand of dispersion of solid particles in different polar media. The technical characteristics are as follows: first, ester monomer copolymerizes under initiator action to prepare a polyester chain segment of random structure, then the polyester chain segment and one of methacrylic acid and acrylic acid copolymerize to prepare carboxyl terminated polyester compound, at last, the carboxyl terminated polyester compound and amine graft react, the obtained solvent chain is polyester, and the anchoring radical is amino or amino and alcohol radical. The invention has the advantages that: 1) the synthesis and preparation of the hyper-dispersant is simple, the production period is short and the cost is low. 2) The hyper-dispersant has good amphipathic structure. Inorganic powder that is modified by the hyper-dispersant shows good amphipathic performance can satisfy the demand of dispersion of the powder in different polar media, thus popularizing the application range of the modified powder and reducing the material processing cost.
Description
Technical field
The present invention relates to a kind of polyester type amphipathic nature ultra-dispersant and preparation method thereof, to satisfy the needs that solid particle disperses in the opposed polarity medium.
Background technology
Along with the swift and violent rise of industrial materials prices, research has attracted a large amount of researchers' sight for Surface Modification Of Inorganic Fillers.For the modification of inorganic filler powder, reduce the reunion between the powder granule, improve the dispersive property of filler powder in resin, improve the melt fluidity that adds man-hour, and the physical property of finally promoting the filler plastics, be the powder-modified purpose of filler.In order to adapt to the dispersion needs of filler powder in medium, development in recent years one class in polymer type hyper-dispersant.Compare with traditional dispersant, the design feature of hyper-dispersant be an end can with treat dispersed solids particle surface strong bonded, be called the anchoring base, the other end and decentralized medium have better compatibility, are called solvent chain.
The hyper-dispersant that uses mainly contains polyester-type and polyether-type two class hyper-dispersants at present.Existing polyester type ultra-dispersant agent generally is used for the organic media of low polarity or middle polarity.As U.S. Pat 3996059, only be suitable for solid particle and in nonpolar or low polarizable medium, disperse, it is good that CN1146371A is used in middle polarity medium dispersion effect, and GB2153804 also only has good dispersion effect in low polarity and middle polarity medium.And the polyether-type hyper-dispersant generally is used for water-based or strong polarizable medium, as US4398955 and CN101069827A.Above-mentioned hyper-dispersant is not suitable for using in the opposed polarity medium.
Summary of the invention
The technical problem that solves
For fear of the deficiencies in the prior art part, the present invention proposes a kind of polyester type amphipathic nature ultra-dispersant and preparation method thereof, polyester with low polarity is its solvent chain, with the amido of strong polarity or amido and alcohol radical is its anchoring base, thereby give its good amphiphilic nature, can satisfy the needs that solid particle disperses in the opposed polarity medium.
Technical scheme
Basic thought of the present invention is: be reaction monomers with in methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate and the butyl methacrylate two or more at first, copolymerization under action of evocating, make a kind of polyester segment of disordered structure, and then with methacrylic acid or acrylic acid in a kind ofly carry out copolyreaction, make the terminal carboxyl polyester compounds, at last in polyesters compound and ethylenediamine, monoethanolamine, diethanol amine, diethylenetriamine, triethylene tetramine and the TEPA one or more are carried out graft reaction.The solvent chain of the hyper-dispersant that so makes is a lipophile polyester segment preferably, and the anchoring base is hydrophilic amido, alcohol radical.
Polyester type amphipathic nature ultra-dispersant of the present invention, its technical characterictic is: with Ester and methacrylic acid or acrylic acid is comonomer, is grafted monomers with the amine substance, carries out radical polymerization with thermal initiator or redox initiator; Ester is 2.27:1～9:1 with the ratio of methacrylic acid or acrylic acid amount of substance in the described comonomer, and the ratio of Ester and the amount of substance of amine substance should be 18:1～6:1; The addition of described initator is 2.5%～4% of a reaction monomers gross mass; Described reaction monomers gross mass is the comonomer of participation reaction and the gross mass of grafted monomers.
Described Ester is one or more in methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate or the butyl methacrylate.
Described amine substance is one or more in ethylenediamine, monoethanolamine, diethanol amine, diethylenetriamine, triethylene tetramine or the TEPA.
A kind of method for preparing polyester type amphipathic nature ultra-dispersant is characterized in that step is as follows:
Step 1: after the distilled water that quality in the container is about 2 times of reaction monomers gross masses is heated to 50～80 ℃, add 2.5%～4% initator of reaction comonomer gross mass, stir and make initator dissolve fully;
Step 2: add the ester reaction monomer, isothermal reaction 2h;
Step 3: add methacrylic acid or acrylic acid, continue isothermal reaction 2h;
Step 4: drip amine substance, add the back and continue reaction 3～4h, stop reaction afterwards, and take out synthetic product;
Step 5:, obtain the polyester type amphipathic nature ultra-dispersant of upper strata oily liquid with the synthetic product static layering of step 4.
Beneficial effect
The advantage of polyester type amphipathic nature ultra-dispersant that the present invention proposes and preparation method thereof is: 1) synthesis and preparation process of hyper-dispersant is simple, and is with short production cycle, and cost is lower.2) hyper-dispersant of the present invention has good amphiphilic structure.Inorganic particle through this hyper-dispersant modification has embodied good amphiphilic performance, can satisfy the dispersion needs of powder in the opposed polarity medium, thereby has promoted the scope of application of modified powder, has reduced the processing cost of material.
Description of drawings
The hyper-dispersant addition that Fig. 1: embodiment 1 obtains not simultaneously, the oil factor change curve of Paris white
The hyper-dispersant addition that Fig. 2: embodiment 1 obtains not simultaneously, the viscosity change curve of Paris white in atoleine
The hyper-dispersant addition that Fig. 3: embodiment 1 obtains is 4 ‰ o'clock, the viscosity relation curve of modification and unmodified Paris white and atoleine
The hyper-dispersant addition that Fig. 4: embodiment 1 obtains is 4 ‰ o'clock, the viscosity relation curve of modification and unmodified Paris white and water
The hyper-dispersant addition that Fig. 5: embodiment 7 obtains is 5 ‰ o'clock, the viscosity relation curve of modification and unmodified zinc oxide and atoleine
The hyper-dispersant addition that Fig. 6: embodiment 7 obtains is 5 ‰ o'clock, the viscosity relation curve of modification and unmodified zinc oxide and water
The hyper-dispersant addition that Fig. 7: embodiment 7 obtains is 4 ‰ o'clock, the tangent plane SEM figure of modification and unmodified calcium carbonate and polyvinyl resin blend.
(a) be unmodified calcium carbonate: PE=3: 7,
(b) be modified calcium carbonate: PE=3: 7,
(c) be unmodified calcium carbonate: PE=4: 6,
(d) be modified calcium carbonate: PE=4: 6,
(e) be unmodified calcium carbonate: PE=5: 5,
(f) be modified calcium carbonate: PE=5: 5.
The specific embodiment
Now in conjunction with the embodiments, accompanying drawing is further described the present invention:
Embodiment 7 takes by weighing methyl methacrylate 19.2285g, butyl methacrylate 2.6849g, methacrylic acid 7.1667g and triethylene tetramine 3.5123g respectively.Corresponding mol ratio is 8:1:3.44:1, adds 60g distilled water in the four-hole reaction bulb of 250mL, and heats with water-bath.When temperature is elevated to 80 ℃, add 0.7040gKPS.Open stirring, after KPS dissolves fully, drip methyl methacrylate, butyl methacrylate mix monomer with the constant voltage dropper.Mix monomer adds, and begins dropwise addition of acrylic acid behind the isothermal reaction 2h, treat that acrylic acid adds and isothermal reaction 2h after begin to drip diethylenetriamine, after treating that diethylenetriamine is reinforced and finishing, continue reaction 4h, stop reaction afterwards.With the products therefrom separatory, then the upper strata oily liquid is desired hyper-dispersant, is designated as H-7.
Embodiment 8 takes by weighing methyl methacrylate 19.2285g, butyl acrylate 2.4035g, methacrylic acid 2.0900g and monoethanolamine 2.1967g respectively.Corresponding mol ratio is 8:1:1:1.5, adds 52g distilled water in the four-hole reaction bulb of 250mL, and heats with water-bath.When temperature is elevated to 80 ℃, add 0.6500g KPS.Open stirring, after KPS dissolves fully, drip methyl methacrylate, butyl methacrylate mix monomer with the constant voltage dropper.Mix monomer adds, and begins to drip methacrylic acid behind the isothermal reaction 2h, treat that methacrylic acid adds and isothermal reaction 2h after begin to drip monoethanolamine, after treating that monoethanolamine is reinforced and finishing, continue reaction 4h, stop reaction afterwards.With the products therefrom separatory, then the upper strata oily liquid is desired hyper-dispersant, is designated as H-8.
Above-mentioned dispersant effect is exemplified below:
(1) getting quality 0,0.1,0.2,0.3,0.4,0.5 and the 0.6g of the hyper-dispersant H-1 that embodiment 1 makes, is that 1500 purpose powdered whitings mix with seven parts of order numbers respectively, and every part of calcium carbonate quality is 100g.With the high speed gyratory shaker calcium carbonate mixture is carried out dry method modification and handle, intermittently stir process 1min divides and finishes for 9 times.Pressing GB1712-79 measures the oil factor of gained calcium carbonate and measures the viscosity of calcium carbonate in the atoleine system with NDJ-79 type rotational viscometer with linseed oil.
The result shows, compares with unmodified calcium carbonate, and calcium carbonate oil factor after the hyper-dispersant modification significantly reduces, and the viscosity in atoleine also descends significantly.See Fig. 1 and Fig. 2.
(2) hyper-dispersant H-1, the H-2, H-3, H-4, H-5, H-6, H-7, the H-8 that make of embodiment 1,2,3,4,5,6,7,8 respectively gets quality 0.4g, be that the several 1500 purpose powdered whitings of 100g order mix with 8 parts of quality respectively, with the high speed gyratory shaker calcium carbonate mixture being carried out dry method modification handles, intermittently stir process 1min divides and finishes for 9 times.Press GB1712-79 measures Paris white with linseed oil oil factor.
The result shows, compares with unmodified calcium carbonate, and calcium carbonate is after the hyper-dispersant modification, oil factor significantly reduces, and when hyper-dispersant modification that calcium carbonate makes with different embodiments, its oil factor is variant, but difference is little, and this illustrates that prepared hyper-dispersant effect is all fine, sees Table 1.
(3) the quality 0.4g that gets the hyper-dispersant H-1 that embodiment 1 makes mixes with 100g1500 purpose powdered whiting, with the high speed gyratory shaker calcium carbonate mixture is carried out dry method modification and handles, and intermittently stir process 1min divides and finishes for 9 times.Measure unmodified calcium carbonate, the viscosity of modified calcium carbonate in atoleine system and aqueous systems respectively with NDJ-79 type rotational viscometer.
The result shows, compares with unmodified calcium carbonate, and calcium carbonate is after the hyper-dispersant modification, and the viscosity in atoleine and aqueous systems obviously descends, and along with the increase decline scope of calcium carbonate content in the system increases, sees Fig. 3 and Fig. 4.
(4) the quality 0.5g that gets the hyper-dispersant H-6 that embodiment 6 makes mixes with the nano level zinc oxide of 100g, with the high speed gyratory shaker zinc oxide mixture is carried out dry method modification and handles, and intermittently stir process 1min divides and finishes for 9 times.Measure unmodified zinc oxide, the viscosity of modified zinc oxide in atoleine system and aqueous systems respectively with NDJ-79 type rotational viscometer.
The result shows, compares with unmodified zinc oxide, and zinc oxide is after the hyper-dispersant modification, and the viscosity in atoleine and aqueous systems significantly descends, and along with the increase decline scope of zinc oxide content in the system is bigger, sees Fig. 5 and Fig. 6.
(5) the quality 0.8g that gets the hyper-dispersant H-6 that embodiment 6 makes mixes with 200g1500 purpose powdered whiting, with the high speed gyratory shaker calcium carbonate mixture is carried out dry method modification and handles, and intermittently stir process 1min divides and finishes for 9 times.
Adopt X (S) K-160 open refining glue of type (moulding) roller refining machine, unmodified calcium carbonate and modified calcium carbonate are filled into respectively in the LDPE resin.The proportioning of calcium carbonate and LDPE is 3:7,4:6,5:5.With the CaCO that obtains
3/ LDPE mixture is watched tangent plane with SEM.The result shows, compare with unmodified calcium carbonate, calcium carbonate after the hyper-dispersant modification, CaCO
3/ LDPE co-mixing system does not have calcium carbonate to expose particle, does not have the calcium carbonate particle of cohesion, can't see the boundary defect between calcium carbonate and the LDPE, sees Fig. 7.
The hyper-dispersant that makes according to the method described above, when practical application, its optimum amount is decided by the specific area of dispersed solid particle.Usually consumption can be at 0.5～5.0mg/M
2Choose in the scope.When other factors was constant, viscosity by investigating dispersion or oil factor can be in the hope of the use amounts of best hyper-dispersant with the variation relation of hyper-dispersant consumption, and when optimum amount, the viscosity of dispersion is minimum, oil factor is minimum usually.
The Paris white oil factor of the hyper-dispersant correspondence of the different embodiment preparations of table 1
| Hyper-dispersant | Do not have | H-1 | H-2 | H-3 | H-4 | H-5 | H-6 | H-7 | H-8 |
| Oil factor mL/100g | 28.30 | 20.20 | 20.70 | 21.02 | 21.21 | 20.60 | 20.40 | 20.72 | 20.55 |
In sum, visible hyper-dispersant of the present invention is significant to the surface modification effect of inorganic particle, and powder has good amphipathic after modification, thereby promotes the use of modified calcium carbonate in different medium.
Claims (4)
1. polyester type amphipathic nature ultra-dispersant is characterized in that: with Ester and methacrylic acid or acrylic acid is comonomer, is grafted monomers with the amine substance, carries out radical polymerization with thermal initiator or redox initiator; Ester is 2.27:1～9:1 with the ratio of methacrylic acid or acrylic acid amount of substance in the described comonomer, and the ratio of Ester and the amount of substance of amine substance should be 18:1～6:1; The addition of described initator is 2.5%～4% of a reaction monomers gross mass; Described reaction monomers gross mass is the comonomer of participation reaction and the gross mass of grafted monomers.
2. polyester type amphipathic nature ultra-dispersant according to claim 1 is characterized in that: described Ester is one or more in methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate or the butyl methacrylate.
3. polyester type amphipathic nature ultra-dispersant according to claim 1 is characterized in that: described amine substance is one or more in ethylenediamine, monoethanolamine, diethanol amine, diethylenetriamine, triethylene tetramine or the TEPA.
4. method for preparing any polyester type amphipathic nature ultra-dispersant in the claim 1～3 is characterized in that step is as follows:
Step 1: after the distilled water that quality in the container is about 2 times of reaction monomers gross masses is heated to 50～80 ℃, add 2.5%～4% initator of reaction comonomer gross mass, stir and make initator dissolve fully;
Step 2: add the ester reaction monomer, isothermal reaction 2h;
Step 3: add methacrylic acid or acrylic acid, continue isothermal reaction 2h;
Step 4: drip amine substance, add the back and continue reaction 3～4h, stop reaction afterwards, and take out synthetic product;
Step 5:, obtain the polyester type amphipathic nature ultra-dispersant of upper strata oily liquid with the synthetic product static layering of step 4.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101665557B (en) * | 2009-09-09 | 2011-04-27 | 华东交通大学 | Ultra-dispersion agent for filling modification of polymer materials and preparation method thereof |
| CN108047366A (en) * | 2017-12-14 | 2018-05-18 | 佛山市彩贵新型材料有限公司 | A kind of preparation method of polyacrylate dispersant |
| CN113968967A (en) * | 2020-07-23 | 2022-01-25 | 赢创运营有限公司 | Polyamide amine dispersants |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1115351C (en) * | 1999-08-31 | 2003-07-23 | 中国石油化工集团公司 | Process for preparing graft copolymerization type non-ash disperser |
| FR2877670B1 (en) * | 2004-11-09 | 2007-02-02 | Arkema Sa | WATER-SOLUBLE ACRYLIC DISPERTERS OBTAINED BY CONTROLLED RADICAL POLYMERIZATION |
| CN1330405C (en) * | 2005-10-21 | 2007-08-08 | 上海东升新材料有限公司 | A sort of dispersant and application |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101665557B (en) * | 2009-09-09 | 2011-04-27 | 华东交通大学 | Ultra-dispersion agent for filling modification of polymer materials and preparation method thereof |
| CN108047366A (en) * | 2017-12-14 | 2018-05-18 | 佛山市彩贵新型材料有限公司 | A kind of preparation method of polyacrylate dispersant |
| CN113968967A (en) * | 2020-07-23 | 2022-01-25 | 赢创运营有限公司 | Polyamide amine dispersants |
| CN113968967B (en) * | 2020-07-23 | 2024-02-06 | 赢创运营有限公司 | Polyamide amine dispersants |
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