CN1482172A - polyacrylic ester/inorganics I/inorganics II ternary compound particle and process for producing the same - Google Patents

polyacrylic ester/inorganics I/inorganics II ternary compound particle and process for producing the same Download PDF

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CN1482172A
CN1482172A CNA031354556A CN03135455A CN1482172A CN 1482172 A CN1482172 A CN 1482172A CN A031354556 A CNA031354556 A CN A031354556A CN 03135455 A CN03135455 A CN 03135455A CN 1482172 A CN1482172 A CN 1482172A
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inorganics
composite particles
polyacrylic ester
deionized water
binary
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CN1240768C (en
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宜 淡
淡宜
江龙
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Sichuan University
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Sichuan University
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Abstract

The present invention features that inorganic matter I produced with matter an and matter B through in-situ reaction in hydrosol of porous inorganic matter II and the porous inorganic matter II form the composite binary inorganic matter I/inorganic matter II particle via adsorption; the composite particle is modified with silane coupling agent; the modified composite particle is mixed with acrylate monomer, emulsifier, initiator and deionized water in a three-necked bottle; and the mixture is stirred and heated to 60-80 deg.c for reaction for 3-6 hr before being lowered in temperature and discharged. After precipitation in water solution of calcium chloride of 1-10 % concentration, repeated washing with deionized water to eliminate emulsifier and vacuum stoving at 50 deg.c, the ternary composite polyacrylate/inorganic matter I/ inorganic matter II particle with relatively strong mutual effect is obtained.

Description

Polyacrylic ester/inorganics I/ inorganics II ternary composite particles and preparation method thereof
One, technical field
The present invention relates to a kind of polyacrylic ester/inorganics I/ inorganics II ternary composite particles and preparation method thereof, belong to the preparation field of polymer composites.
Two, background technology
At present, the preparation method of polymer/inorganic thing matrix material mainly contains following several:
1, the direct blend of polymkeric substance and inorganic particulate (engineering plastics are used for Hu Ping, Fan Shoushan etc., and 1998,26 (1): 1; S.Maede, S.P.Armes, Synth.Meta., 1995,73:151).This method is because preparation is simple, and is easy to operate and be widely used, but polymkeric substance, inorganic particulate two are alternate easily separated, causes the degradation of material.Though can improve the biphase consistency by modification is carried out on the inorganic particulate surface, the stability of material still is not fine.
2, polymkeric substance parcel inorganic particulate method, as prepare polymer/inorganic thing matrix material (Masahiro Haregawa, Kunio Arai, Shozaburo Saito by the emulsifier-free emulsion polymerization method, J.Appl Polym Sci, 1987,33:411-418, M.Hasegawa, K.Arai, S.Satio, J.Polym.Sci.Part A:Polym.Chem.1982,20:1021-1029).Utilize this method to superscribe polymer layer, but the reactive force between polymkeric substance and the inorganics is a physical force, easily is separated on the inorganic particulate surface.
3, sol-gel processing (Hong Weiliang, Liu Jianhong etc., chemical research and application, 2000,12 (2): 132; Y.Mizutani, S.Nago.J.Appl.Polym.Sci, 1999,72:1489).It is less to make particle diameter by this method, and inorganic particulate is finely dispersed composite particles in polymkeric substance, but will use a large amount of solvents, and solvent has stronger selectivity to inorganic particulate and polymer monomer.
4, organic monomer forms polymer/inorganic thing matrix material (N.Tusbokawa, K.Maruyama, Y.Sone, Polym.J, 1989,21:133-144 in the polymerization of inorganic particulate surface in situ; Hongquan Xie, Yongmei Ma.J.ApplPolym Sci, 2000,76:845).Can prepare the polymer/inorganic thing matrix material that has than strong interaction by this method, but inorganic particulate select for use scope narrower, for surface chemistry inert inorganic particulate,, just be difficult to preparation and have polymer/inorganic thing matrix material than strong interaction such as lime carbonate etc.
All there is such deficiency in above several method except having characteristics separately: the composite particles of preparation generally all only relates to the compound of single polymers and single inorganics, is difficult to give full play to the structure of composite particles and have complementary functions.
Three, summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of polymer/inorganic thing I/ inorganics II ternary composite particles and preparation method thereof is provided.
Purpose of the present invention is realized that by following technical measures wherein said raw material umber is parts by weight except that specified otherwise.
The recipe ingredient of polyacrylic ester/inorganics I/ inorganics II ternary composite particles is:
Acrylic ester monomer 5-35 part
Inorganics I/ inorganics II binary composite particles 5-35 part
0.025～2.5 part of silane coupling agent
1～3 part of emulsifying agent
0.01～1.5 part of initiator
80～100 parts of deionized waters
Acrylic ester monomer is at least a in methyl methacrylate, butyl acrylate, methyl acrylate and/or the ethyl propenoate;
Inorganics I is a lime carbonate in the inorganics I/ inorganics II binary composite particles, barium sulfate, and at least a in titanium oxide or the calcium sulfate, inorganics II is porous, functionalisable inorganics silicon-dioxide or disilicon trioxide.
Emulsifying agent is at least a in sodium lauryl sulphate, sodium laurylsulfonate and/or the Sodium dodecylbenzene sulfonate.
Initiator is a kind of in Potassium Persulphate, ammonium persulphate or the redox initiation system.
The preparation method of polyacrylic ester/inorganics I/ inorganics II ternary composite particles:
(1) preparation of inorganics I/ inorganics II unit composite particles
Take by weighing functionalisable porous, inorganic thing II1-5 part by weight, have in the three-necked bottle of thermometer, agitator and dropping funnel the adding of deionized water 10-30 part, be warming up to 40-60 ℃, stir and form the inorganics II water-sol, press and took by weighing inorganic reaction thing A and inorganic reaction thing B in 1: 1 to 10: 1 respectively, and respectively its dissolving is formed solution with appropriate amount of deionized water with functionalisable porous, inorganic thing II mol ratio.At first inorganics A solution 0.1-0.3mol/L is joined in the aforementioned inorganics II colloidal sol, in reactor, slowly drip inorganics B aqueous solution 0.3-0.5mol/L by dropping funnel then, after waiting to drip fully, at 40-60 ℃ of following constant temperature, stirred 3-5 hour, last cooling discharge, with products therefrom through the deionized water thorough washing, remove by product, dry, grinding makes inorganics I/ inorganics II binary composite particles;
(2) surface modification of inorganics I/ inorganics II binary composite particles
Take by weighing dehydrated alcohol 20-50 part by weight, inorganics I/ inorganics II binary composite particles 10-20 part, silane coupling agent 0.1-1 part joins in the equipment of ditto (1), stirring is warming up to 50-60 ℃, reacted cooling discharge, the solvent in vacuum pump suction filtration removal system 4-8 hour, and use ethanol drip washing, remove unreacted surface-modifying agent.In temperature 50-70 ℃ of following dry for standby;
(3) preparation of polyacrylic ester/inorganics I/ inorganics II ternary composite particles
Take by weighing inorganics I/ inorganics II binary composite particles 5-35 part of above-mentioned surface modification by weight, acrylate 5-35 part, emulsifying agent 1-3 part, initiator 0.01-1.5 part, deionized water 80-100 part, add and have thermometer, in the three-necked bottle of agitator and reflux exchanger, stir, be warming up to 60-80 ℃, reacted 3-6 hour, cooling discharge precipitates with the 1-10% calcium chloride water then, and removes emulsifying agent with the deionized water repetitive scrubbing, 60-70 ℃ of following vacuum drying obtains to have the polyacrylic ester/inorganics I/ inorganics II ternary composite particles than strong interaction.
The present invention has following advantage:
1, the chemical reaction by binary inorganics in the porous granule prepares the inorganic compounding particle, realize between inorganics and the inorganics structure with have complementary functions.Then, the conventional emulsion polymerization that carries out acrylic ester monomer in the presence of functionalized inorganic compounding particle has prepared polyacrylic ester/inorganics I/ inorganics II multi-element composite material, further realized between polymkeric substance and the inorganics structure with have complementary functions.
2, by the functionalisable chemically inert inorganic particulate of inorganic particulate adsorption surface of porous, and further with the acrylic ester monomer copolymerization, preparation has polymer/inorganic thing composite particles than strong interaction at polymer molecule and inorganics molecule, has developed the preparation method of polymer/inorganic thing composite particles.
3, adopt conventional emulsion polymerization, method is simple, and cost is low, helps realizing industrialization.
Four, description of drawings
Fig. 1 is PMMA and CaCO 3/ SiO 2The infrared spectrogram of binary composite particles blend
Fig. 2 is PMMA/CaCO 3/ SiO 2The infrared spectrogram of ternary composite particles
Fig. 3 is PMMA/CaCO 3/ SiO 2The thermogravimetric curve of ternary composite particles
In the infrared spectrogram of Fig. 1 at 1733cm -1The place does not find the charateristic avsorption band of carbonyl among the PMMA, in the infrared spectrogram of Fig. 2 at 1733cm -1The place has found this charateristic avsorption band, and this proves PMMA/CaCO 3/ SiO 2Some PMMA is with stronger interaction and CaCO in the ternary composite particles 3/ SiO 2The relative mass content that the effect of binary composite particles, the thermogravimetric curve of Fig. 3 have further provided this part PMMA is 13%.
Five, embodiment
Below by embodiment the present invention is specifically described; be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
Embodiment 1:
(1) with silicon-dioxide 30g, deionized water 300g adds and has in the three-necked bottle of thermometer, agitator and dropping funnel, is warming up to 50 ℃, stirs 10min, forms silica hydrosol.Get calcium chloride 55.5g, yellow soda ash 53g forms solution with 100g, 300g deionized water dissolving respectively.Sodium carbonate solution is added in the above-mentioned silicon dioxide gel, press speed dropping calcium chloride solution in this system of 0.5g/min then by dropping funnel.After dripping fully, isothermal reaction 2 hours, cooling discharge then.Vacuum filtration separates, and with deionized water repetitive scrubbing precipitation, removes the NaCl that generates.Promptly obtain CaCO 60 ℃ of oven dry 3/ SiO 2The binary composite particles.Method by BET is tested CaCO respectively 3, SiO 2, CaCO 3/ SiO 2Binary composite particles and CaCO 3With SiO 2The specific surface area of blend and pore volume, detailed being shown in Table 1.As seen from Table 1, CaCO 3/ SiO 2The specific surface area of binary composite particles is 36.5m 2/ g, this not only is far smaller than SiO 2The specific surface area 223.6m of particle 2/ g, and less than CaCO 3With SiO 2The specific surface area 81.8m of blend 2/ g, this shows the CaCO that reaction generates 3Particle enters porous SiO 2In the particle hole, form the CaCO of interstitital texture 3/ SiO 2The binary composite particles.CaCO 3Particle and SiO 2The variation of the average pore volume in the compound front and back of particle has also proved this fact.
(2) take by weighing the CaCO for preparing gained by (1) 3/ SiO 2Binary composite particles 25g, silane coupling agent 1.25g, ethanol 75g adds and has in the three-necked bottle of thermometer, agitator and reflux exchanger, is warming up to 50 ℃, stirs discharging then 6 hours.Vacuum filtration is removed ethanol, and removes unreacted silane coupling agent with alcohol flushing, and in 50 ℃ of oven dry down of temperature, porphyrize obtains modification CaCO 3/ SiO 2The binary composite particles.
(3) in the equipment identical, add the modification CaCO for preparing gained by (2) successively with (2) 3/ SiO 2Binary composite particles 20g, sodium lauryl sulphate 0.8g, deionized water 80g is warming up to 40 ℃ and stirred 20 minutes; Add methyl methacrylate 20g then successively, Potassium Persulphate 0.2g.Be warming up to 80 ℃ after 20 minutes, isothermal reaction 4 hours, cooling discharge.With 10% calcium chloride solution precipitation, and, can obtain product in 50 ℃ of following oven dry of temperature with deionized water repetitive scrubbing precipitation.With products therefrom in Soxhlet extractor through trichloromethane backflow extracting 5-7 days, remove the homopolymerization polymethylmethacrylate, in temperature 50-70 ℃ vacuum drying, the product of acquisition carries out infrared test and thermogravimetic analysis (TGA) (TGA) test respectively then, and its result sees for details shown in Fig. 2～3.
Embodiment 2:
(1) by step and the formulation CaCO identical with embodiment 1 (1) 3/ SiO 2The binary composite particles.
(2) take by weighing the CaCO for preparing gained by (1) 3/ SiO 2Binary composite particles 10g, silane coupling agent 0.5g, ethanol 30g adds and has in the three-necked bottle of thermometer, agitator and reflux exchanger, is warming up to 50 ℃, stirs discharging then 6 hours.Vacuum filtration is removed ethanol, and removes unreacted silane coupling agent with alcohol flushing.In 50 ℃ of oven dry of temperature, porphyrize obtains modification CaCO 3/ SiO 2The binary composite particles.
(3) in above-mentioned equipment, add the modification CaCO for preparing gained by (2) successively 3/ SiO 2Binary composite particles 10g, sodium lauryl sulphate 0.8g, deionized water 80g is warming up to 40 ℃ and stirred 20 minutes; Add butyl acrylate 30g then successively, redox initiator 0.3g.Be warming up to 65 ℃ after 20 minutes, isothermal reaction 6 hours, cooling discharge.With 10% calcium chloride solution precipitation, and with deionized water repetitive scrubbing precipitation, in 50 ℃ of oven dry of temperature, acquisition product.
Embodiment 3:
(1) with silicon-dioxide 6g, deionized water 100g adds and has in the three-necked bottle of thermometer, agitator and dropping funnel, is warming up to 50 ℃, stirs 10min, forms silica hydrosol.Get calcium chloride 55.5g, yellow soda ash 53g forms solution with 100g, 300g deionized water dissolving respectively.Sodium carbonate solution is added in the above-mentioned silicon dioxide gel, press speed dropping calcium chloride solution in this system of 0.5g/min then by dropping funnel.After dripping fully, isothermal reaction 2 hours, cooling discharge then.Vacuum filtration separates, and with deionized water repetitive scrubbing precipitation, removes the NaCl that generates.Promptly obtain CaCO 60 ℃ of oven dry 3/ SiO 2The binary composite particles.
(2) by step identical and prescription modification CaCO with embodiment 1 (2) 3/ SiO 2The binary composite particles.
(3) get the modification CaCO for preparing gained by (2) 3/ SiO 2Binary composite particles 20g joins and is equipped with in 10g butyl acrylate and the monomeric beaker of 10g methyl methacrylate blend, sealing, soaked into 12 hours, in it being joined the equipment identical with (2), add sodium lauryl sulphate 0.8g then successively, deionized water 80g is warming up to 40 ℃ and stirred 20 minutes; Add Potassium Persulphate 0.3g then.Be warming up to 80 ℃ after 20 minutes, isothermal reaction 6 hours, cooling discharge.With 10% calcium chloride solution precipitation, and with deionized water repetitive scrubbing precipitation, in 50 ℃ of oven dry of temperature, acquisition product.
Embodiment 4
(1) by step and the formulation CaCO identical with embodiment 1 (1) 3/ SiO 2The binary composite particles.
(2) by step identical and prescription modification CaCO with embodiment 1 (2) 3/ SiO 2The binary composite particles.
(3) add modification CaCO in the three-necked bottle that has thermometer, agitator and reflux exchanger successively by (2) preparation gained 3/ SiO 2Binary composite particles 20g, sodium laurylsulfonate 0.8g, deionized water 80g is warming up to 40 ℃ and stirred 20 minutes; Add methyl acrylate 20g then successively, Potassium Persulphate 0.2g.Be warming up to 80 ℃ after 20 minutes, isothermal reaction 4 hours, cooling discharge.With 10% calcium chloride solution precipitation, and with deionized water repetitive scrubbing precipitation, in 50 ℃ of oven dry down of temperature, acquisition product.The specific surface area of table 1 a binary composite particles and an elementary particle and binary blend particle and average pore volume comparison sheet
Sample specific surface area (m 2/ g) average pore volume (cm 3/ g)
SiO 2Particle 223.6 0.42
CaCO 3Particle 3.4 0.01
CaCO 3/ SiO 2Binary composite particles 36.5 0.09
CaCO 3With SiO 2Blend 81.8 0.18

Claims (6)

1, polyacrylic ester/inorganics I/ inorganics II ternary composite particles is characterized in that the recipe ingredient (by weight) of this composite particles is:
Acrylic ester monomer 5-35 part
Inorganics I/ inorganics II binary composite particles 5-35 part
0.025～2.5 part of silane coupling agent
1～3 part of emulsifying agent
0.01～1.5 part of initiator
80～100 parts of deionized waters
2, polyacrylic ester as claimed in claim 1/inorganics I/ inorganics II ternary composite particles is characterized in that acrylic ester monomer is at least a in methyl methacrylate, butyl acrylate, methyl acrylate and/or the ethyl propenoate.
3, polyacrylic ester as claimed in claim 1/inorganics I/ inorganics II ternary composite particles is characterized in that inorganics I is a lime carbonate in the inorganics I/ inorganics II binary composite particles, barium sulfate, at least a in titanium oxide and/or the calcium sulfate; Inorganics II is porous, functionalisable silicon-dioxide or aluminium sesquioxide.
4, polyacrylic ester as claimed in claim 1/inorganics I/ inorganics II ternary composite particles is characterized in that emulsifying agent is at least a in sodium lauryl sulphate, sodium laurylsulfonate and/or the Sodium dodecylbenzene sulfonate.
5, polyacrylic ester as claimed in claim 1/inorganics I/ inorganics II ternary composite particles is characterized in that initiator is a kind of in Potassium Persulphate, ammonium persulphate or the redox initiation system.
6, as the preparation method of the described polyacrylic ester of claim 1～5/inorganics I/ inorganics II ternary composite particles, it is characterized in that:
(1) preparation of inorganics I/ inorganics II binary composite particles
Take by weighing functionalisable porous, inorganic thing II1-5 part by weight, have thermometer the adding of deionized water 10-30 part, in the three-necked bottle of agitator and dropping funnel, be warming up to 40-60 ℃, stir and form the inorganics II water-sol, by taking by weighing equimolar inorganic reaction thing A and inorganic reaction thing B in 1: 1 to 10: 1 respectively with functionalisable porous, inorganic thing II mol ratio, and respectively its dissolving is formed solution with appropriate amount of deionized water, at first inorganics A solution 0.1-0.3mol/L is joined in the aforementioned inorganics II colloidal sol, in reactor, slowly drip inorganics B aqueous solution 0.3-0.5mol/L by dropping funnel then, after waiting to drip fully, at 40-60 ℃ of following constant temperature, stirred 3-5 hour, last cooling discharge, with products therefrom through the deionized water thorough washing, remove by product, drying, grinding makes inorganics I/ inorganics II binary composite particles;
(2) surface modification of inorganics I/ inorganics II binary composite particles
Take by weighing dehydrated alcohol 20-50 part by weight, inorganics I/ inorganics II binary composite particles 10-20 part, silane coupling agent 0.1-1 part joins in the equipment of ditto (1), stirring is warming up to 50-60 ℃, reacts cooling discharge 4-8 hour, solvent in vacuum pump suction filtration removal system, and use ethanol drip washing, remove unreacted surface-modifying agent, in temperature 50-70 ℃ of following dry for standby;
(3) preparation of polyacrylic ester/inorganics I/ inorganics II ternary composite particles
Take by weighing inorganics I/ inorganics II binary composite particles 5-35 part of above-mentioned surface modification by weight, acrylate monomer 5-35 part, emulsifying agent 1-3 part, initiator 0.01-1.5 part, deionized water 80-100 part, add and have thermometer, in the three-necked bottle of agitator and reflux exchanger, stir, be warming up to 60-80 ℃, reacted 3-6 hour, then cooling discharge, precipitate with the 1-10% calcium chloride water, and remove emulsifying agent with the deionized water repetitive scrubbing, 60-70 ℃ of following vacuum drying obtains to have the polyacrylic ester/inorganics I/ inorganics II ternary composite particles than strong interaction.
CN 03135455 2003-07-22 2003-07-22 polyacrylic ester/inorganics I/inorganics II ternary compound particle and process for producing the same Expired - Fee Related CN1240768C (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102964511A (en) * 2012-12-05 2013-03-13 山东世拓高分子材料股份有限公司 Nano barium sulfate impact resistant modified acrylate polymer and preparation method thereof
CN103910821A (en) * 2014-03-14 2014-07-09 中科院广州化学有限公司南雄材料生产基地 A high-pressure-resistant water-permeable porous material and a preparation method thereof
CN111286085A (en) * 2020-02-28 2020-06-16 东华大学 Lipophilic polyacrylate coated calcium carbonate composite material and preparation and application thereof
CN114605763A (en) * 2022-03-18 2022-06-10 江苏全真光学科技股份有限公司 Wear-resistant optical lens ingredient

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102964511A (en) * 2012-12-05 2013-03-13 山东世拓高分子材料股份有限公司 Nano barium sulfate impact resistant modified acrylate polymer and preparation method thereof
CN103910821A (en) * 2014-03-14 2014-07-09 中科院广州化学有限公司南雄材料生产基地 A high-pressure-resistant water-permeable porous material and a preparation method thereof
CN103910821B (en) * 2014-03-14 2016-08-17 中科院广州化学有限公司南雄材料生产基地 A kind of high pressure resistant water penetration porous material and preparation method thereof
CN111286085A (en) * 2020-02-28 2020-06-16 东华大学 Lipophilic polyacrylate coated calcium carbonate composite material and preparation and application thereof
CN114605763A (en) * 2022-03-18 2022-06-10 江苏全真光学科技股份有限公司 Wear-resistant optical lens ingredient

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