CN103319725A - Unsaturated polyester nano attapulgite material and preparation method thereof - Google Patents
Unsaturated polyester nano attapulgite material and preparation method thereof Download PDFInfo
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- CN103319725A CN103319725A CN 201310259035 CN201310259035A CN103319725A CN 103319725 A CN103319725 A CN 103319725A CN 201310259035 CN201310259035 CN 201310259035 CN 201310259035 A CN201310259035 A CN 201310259035A CN 103319725 A CN103319725 A CN 103319725A
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- unsaturated polyester
- attapulgite
- urethane resin
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- nano attapulgite
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Abstract
The invention relates to an unsaturated polyester nano attapulgite material and a preparation method thereof. The unsaturated polyester nano attapulgite material comprises the following components in percentage by mass: 65.5-82.6% of unsaturated polyester polyurethane resin, 1-2.5% of modified attapulgite, 12-16% of solvent, 1-1.2% of initiator, 0.2-0.25% of accelerator and 1-1.5% of defoaming agent. The preparation method comprises the following steps: adding 1-2.5% of nano attapulgite into a formula amount of solvent, dispersing by ultrasonic mechanical stirring for 2 hours, adding the prepared silane coupling agent KH-560, dispersing by ultrasonic mechanical stirring for 2 hours, adding the unsaturated polyester polyurethane resin, dispersing by ultrasonic mechanical stirring for 4 hours, adding the initiator, accelerator and defoaming agent, and casting to obtain the product.
Description
Technical field
The present invention relates to unsaturated polyester nano Attapulgite material preparation technology.
Background technology
The application of unsaturated polyester ester polyurethane has been stretched over each department, and various method for processing forming are also increasingly mature, and the performance of resin has also been proposed different requirements, has promoted the continuous increase of resin kind, and performance progressively improves.Yet unsaturated polyester urethane also has the shortcoming of himself, and hard and crisp behind the unsaturated polyester curable urethane resin, impact property is poor, and the surface is easy to crack; Wear resistance is also relatively poor, and its practical application is very limited.So need to improve shock resistance, wear resistance and hardness, the intensity of resin, the performance such as heat-resisting, water-fast, fire-retardant, and reduce shrinking percentage, improve the quality of unsaturated polyester urethane resin composite prod, broadened application scope.Attapulgite clay has the good colloidal property such as unique dispersion, heatproof, Salt And Alkali Tolerance and higher adsorption bleaching ability, has certain plasticity-and cohesive force, and it is used widely in all trades and professions.The microstructure of attapulgite has brilliant, the brilliant bundle of rod, three different levels of aggregate.Under realistic application conditions, when microstructure is loose, can effectively bring into play the brilliant best effect of rod.Therefore carry out unsaturated polyester urethane and nano-attapulgite compound, nano-attapulgite and macromolecular chain are with covalent bonds, strengthened the bonding force between nano-attapulgite and the polymkeric substance, and make nano-attapulgite being more evenly distributed in polymkeric substance, more be conducive to giving full play to of nano-attapulgite nano-meter characteristic.This method products obtained therefrom has good corrosion stability, thermotolerance, wear resistance, self-cleaning and the feature of environmental protection.Therefore be subject to paying close attention to widely.
Patent CN102212242A discloses a kind of unsaturated polyester block polymers of polyurethane composite manufacture method, and this technology adopts pickling process that glass fibre is soft to making matrix material, the technique more complicated with the unsaturated polyester urethane resin.
Summary of the invention
The purpose of this invention is to provide a kind of unsaturated polyester nano Attapulgite material and preparation method thereof.
The present invention is unsaturated polyester nano Attapulgite material and preparation method thereof, unsaturated polyester nano Attapulgite material, by mass percentage, total mass based on unsaturated polyester nano Attapulgite material, its component is: unsaturated polyester urethane resin 65.5% ~ 82.6%, modified attapulgite 1% ~ 2.5%, solvent 12% ~ 16%; Initiator 1% ~ 1.2%, promotor 0.2% ~ 0.25%, defoamer 1% ~ 1.5%;
Based on the total mass of unsaturated polyester urethane resin, by mass percentage, the prescription of unsaturated polyester urethane resin is:
Unsaturated polyester resin 76.5% ~ 80%, polyoxyethylene glycol 11.5% ~ 13.5%, 2,4 toluene diisocyanate 4% ~ 8%, vinylbenzene 7% ~ 10%, Resorcinol 0.02%, catalyzer 0.02% ~ 0.03%.
Unsaturated polyester nano Attapulgite material preparation method the steps include:
(1) preparation process of unsaturated polyester urethane resin: take by weighing the unsaturated polyester resin of formula ratio in the there-necked flask of 250ml, then the polyoxyethylene glycol, 2,4 toluene diisocyanate, vinylbenzene, Resorcinol and the catalyzer dibutyl tin laurate that add successively formula ratio; Be put in the water-bath at last and heat, keeping temperature is 80 ℃; Behind the reaction 1h, with dibutylamine-toluene solution and HCl-H
2O solution is surveyed the content of NCO, surveys once every 30min; When the content of NCO is substantially constant, stopped heating, discharging;
(2) attapulgite modified preparation process is: press the formula ratio batching, add pretreated attapulgite in solvent, first ultra-sonic dispersion 2h adds the KH560 solution for preparing again, and dehydrated alcohol accounts for 72% in the solution, and distilled water accounts for 8%, and ultrasonic 2h gets final product;
(3) unsaturated polyester polyurethane nano Attapulgite material preparation step is:
Press the formula ratio batching, at the unsaturated polyester urethane resin of attapulgite modified middle adding metering, then the ultrasonic 4h in mechanical stirring limit, limit adds the initiator methylethyl ketone peroxide, promotor cobalt naphthenate and defoamer methyl-silicone oil, and cast molding gets final product after stirring.
Usefulness of the present invention is, adopt the urethane resin modified unsaturated polyester resin by the Step Condensation method, synthesized the unsaturated polyester urethane resin that contains carbamate groups in the macromolecular chain, then with the attapulgite of modification the unsaturated polyester urethane resin is carried out modification and synthesized nano composite material, synthetic nano composite material can be used as the functional nano matrix materials such as plastics, rubber, fiber and coating, is widely used in the various fields such as building, automobile, household electrical appliances, weaving.
Embodiment
The present invention is finished by following technical scheme, to mix dibasic alcohol, monounsaturated dicarboxylic acid acid anhydride and unsaturated dicarboxylic acid anhydride by the synthetic unsaturated polyester with-OH end-blocking of polycondensation, unsaturated polyester and tolylene diisocyanate obtain unsaturated polyester urethane through addition polymerization progressively, the nano-attapulgite of unsaturated polyester urethane and modification is compound, then adds solidifying agent and initiator and casts and obtain unsaturated polyester urethane nano concavo-convex rod composite material.
Unsaturated polyester urethane nano concavo-convex rod composite material synthesis route is as follows:
Based on the total mass of polyurethane modified unsaturated polyester nano concavo-convex bar material, by mass percentage, unsaturated polyester urethane nano-attapulgite material prescription is:
Unsaturated polyester urethane resin 65.5% ~ 82.6%, attapulgite modified 1% ~ 2.5%, solvent 12% ~ 16%; Initiator 1% ~ 1.2%, promotor 0.2% ~ 0.25%, defoamer 1% ~ 1.5%;
Based on the total mass of unsaturated polyester urethane resin, by mass percentage, the prescription of unsaturated polyester urethane resin is:
Unsaturated polyester resin 76.5% ~ 80%, polyoxyethylene glycol 11.5% ~ 13.5%, 2,4 toluene diisocyanate 4% ~ 8%, vinylbenzene 7% ~ 10%, catalyzer 0.02% ~ 0.03%.
Wherein the unsaturated polyester resin molecular-weight average is between 2000 ~ 2500, and the polyoxyethylene glycol molecular-weight average is 400, and catalyzer is dibutyl tin laurate.
The preparation process of unsaturated polyester urethane resin is as follows: take by weighing the unsaturated polyester resin of formula ratio in the there-necked flask of 250ml, then the polyoxyethylene glycol, 2,4 toluene diisocyanate (TDI), vinylbenzene, Resorcinol and the catalyzer dibutyl tin laurate that add successively formula ratio.Be put in the water-bath at last and heat, keeping temperature is 80 ℃.Behind the reaction 1h, with certain density dibutylamine-toluene solution and HCl-H
2O solution is surveyed the content of NCO, surveys once every 30min.When the content of NCO is substantially constant, stopped heating, discharging.
Attapulgite modified preparation process is: press the formula ratio batching, add pretreated attapulgite in solvent, first ultra-sonic dispersion 2h adds the KH560 solution (wherein dehydrated alcohol accounts for 72%, and distilled water accounts for 8%) for preparing again, and ultrasonic 2h gets final product.
Polyurethane modified unsaturated polyester nano-attapulgite composite manufacture step is: press the formula ratio batching, unsaturated polyester urethane resin in attapulgite modified middle adding metering, the ultrasonic 4h in mechanical stirring limit, limit, then add the initiator methylethyl ketone peroxide, promotor cobalt naphthenate and defoamer methyl-silicone oil, cast molding gets final product after stirring.
Below be embodiments of the invention, but the present invention is not limited in the following example.
The preparation of embodiment 1. unsaturated polyester urethane resins
Take by weighing the unsaturated polyester resin of 85g, the 12.8g polyoxyethylene glycol, 4.7gTDI adds vinylbenzene, 0.039g Resorcinol and 3 dibutyl tin laurates of 8.5g again.These materials are added in the there-necked flask, be put in the water-bath and heat, keeping temperature is 60 ℃.Behind the reaction 1h, survey the content of NCO with dibutylamine-toluene solution and HCl, method is as follows: get the sample about 1g, add 10ml dibutylamine-toluene solution, place 20min under the normal temperature, add again the 50ml industrial spirit, add 3～4 1% tetrabromo-mcresolsulfonphthalein indicator, use 0.5mol/LHCl-H
2Blank assay is done in the titration of O reference liquid simultaneously, and solution is terminal point by blue flavescence green.Survey once every 30min later on.When NCO content is substantially constant, stopped heating, discharging.
Embodiment 2. polyurethane modified unsaturated polyester nano concavo-convex bar material and preparations thereof
Take the 20g unsaturated polyester urethane as benchmark, take by weighing 0.24g pre-treatment attapulgite, add 3g vinylbenzene, ultra-sonic dispersion 2h, (wherein dehydrated alcohol accounts for 72% to add the KH560 solution for preparing again, distilled water accounts for 8%), ultra-sonic dispersion 2h adds the unsaturated polyester urethane resin at last, mechanical stirring limit, limit ultra-sonic dispersion 4h, add 0.26g initiator methylethyl ketone peroxide, 0.05g promotor cobalt naphthenate and 0.26g defoamer methyl-silicone oil, casting namely obtains product after stirring.
Claims (4)
1. unsaturated polyester nano Attapulgite material, by mass percentage, based on the total mass of unsaturated polyester nano Attapulgite material, its component is: unsaturated polyester urethane resin 65.5% ~ 82.6%, modified attapulgite 1% ~ 2.5%, solvent 12% ~ 16%; Initiator 1% ~ 1.2%, promotor 0.2% ~ 0.25%, defoamer 1% ~ 1.5%;
Based on the total mass of unsaturated polyester urethane resin, by mass percentage, the prescription of unsaturated polyester urethane resin is:
Unsaturated polyester resin 76.5% ~ 80%, polyoxyethylene glycol 11.5% ~ 13.5%, 2,4 toluene diisocyanate 4% ~ 8%, vinylbenzene 7% ~ 10%, Resorcinol 0.02%, catalyzer 0.02% ~ 0.03%.
2. unsaturated polyester nano Attapulgite material according to claim 1, it is characterized in that: its solvent that uses is vinylbenzene, and initiator is methylethyl ketone peroxide, and promotor is cobalt naphthenate, and defoamer is methyl-silicone oil.
3. unsaturated polyester nano Attapulgite material according to claim 1, it is characterized in that: wherein the unsaturated polyester resin molecular-weight average is between 2000 ~ 2500, and the polyoxyethylene glycol molecular-weight average is 400, and catalyzer is dibutyl tin laurate.
4. unsaturated polyester nano Attapulgite material preparation method the steps include:
(1) preparation process of unsaturated polyester urethane resin: take by weighing the unsaturated polyester resin of formula ratio in the there-necked flask of 250ml, then the polyoxyethylene glycol, 2,4 toluene diisocyanate, vinylbenzene, Resorcinol and the catalyzer dibutyl tin laurate that add successively formula ratio; Be put in the water-bath at last and heat, keeping temperature is 80 ℃; Behind the reaction 1h, with dibutylamine-toluene solution and HCl-H
2O solution is surveyed the content of NCO, surveys once every 30min; When the content of NCO is substantially constant, stopped heating, discharging;
(2) attapulgite modified preparation process is: press the formula ratio batching, add pretreated attapulgite in solvent, first ultra-sonic dispersion 2h adds the KH560 solution for preparing again, and dehydrated alcohol accounts for 72% in the solution, and distilled water accounts for 8%, and ultrasonic 2h gets final product;
(3) unsaturated polyester polyurethane nano Attapulgite material preparation step is:
Press the formula ratio batching, at the unsaturated polyester urethane resin of attapulgite modified middle adding metering, then the ultrasonic 4h in mechanical stirring limit, limit adds the initiator methylethyl ketone peroxide, promotor cobalt naphthenate and defoamer methyl-silicone oil, and cast molding gets final product after stirring.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104727156A (en) * | 2015-04-09 | 2015-06-24 | 淮阴工学院 | Method for filling and synthetizing full waterborne polyurethane base leather through nano attapulgite |
| CN105837785A (en) * | 2016-06-16 | 2016-08-10 | 上海理工大学 | Preparation method of attapulgite/fluorinated polyurethane nanocomposite |
| CN115197549A (en) * | 2022-06-27 | 2022-10-18 | 合复新材料科技(无锡)有限公司 | Rapid crystallization PET resin of nanometer attapulgite copolymerized PEG and preparation method thereof |
-
2013
- 2013-06-26 CN CN 201310259035 patent/CN103319725A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104727156A (en) * | 2015-04-09 | 2015-06-24 | 淮阴工学院 | Method for filling and synthetizing full waterborne polyurethane base leather through nano attapulgite |
| CN105837785A (en) * | 2016-06-16 | 2016-08-10 | 上海理工大学 | Preparation method of attapulgite/fluorinated polyurethane nanocomposite |
| CN105837785B (en) * | 2016-06-16 | 2018-10-12 | 上海理工大学 | A kind of preparation method of attapulgite/fluorochemical urethane nanocomposite |
| CN115197549A (en) * | 2022-06-27 | 2022-10-18 | 合复新材料科技(无锡)有限公司 | Rapid crystallization PET resin of nanometer attapulgite copolymerized PEG and preparation method thereof |
| CN115197549B (en) * | 2022-06-27 | 2023-12-29 | 山东道恩合复新材料有限公司 | Rapid crystallization PET resin of nano attapulgite copolymerized PEG and preparation method thereof |
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Application publication date: 20130925 |