CN101704962B - Method for preparing chlorinated alkoxy biomass plasticizer - Google Patents
Method for preparing chlorinated alkoxy biomass plasticizer Download PDFInfo
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- CN101704962B CN101704962B CN2009101939035A CN200910193903A CN101704962B CN 101704962 B CN101704962 B CN 101704962B CN 2009101939035 A CN2009101939035 A CN 2009101939035A CN 200910193903 A CN200910193903 A CN 200910193903A CN 101704962 B CN101704962 B CN 101704962B
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Abstract
The invention provides a method for preparing chlorinated alkoxy biomass plasticizer. The method comprises the following steps: selecting biodiesel with iodine value between 50 and 120; ensuring that the weight ratio of biodiesel to organic alcohol to catalyst to chlorine gas to stabilizing agent is 100:5-30:0.05-0.2:20-50:0.2-0.4; adding the biodiesel, the organic alcohol and the catalyst to a reactor; heating materials to between 40 and 60 DEG C in a mixing state; supplying the chlorine gas to a reaction system at a speed controlled in a range between 40 and 60 kg/h for 2.5 to 4 hours; ensuring that the total chlorine amount is 20 to 50 percent of the weight of the biodiesel; completing chlorine supply and using dry air to blow out HCI dissolved in the materials in the reactor for deacidification refining; adding the stabilizing agent; and obtaining a product. The method has the advantages of simplicity, low cost, good compatibility with PVC, good plasticizing effects, low volatility, low migration property, good cold resistance and good stabilizing effect on light and heat, and the plasticizer is a compound plasticizer which is resistant to flame, free from toxicity and friendly to environment.
Description
Technical field
The invention belongs to polymeric material field, particularly softening agent and preparation method thereof field is specifically related to the preparation method of chloro type softening agent.
Background technology
The softening agent that adds certain ratio in the macromolecule resin material can improve and improve the processing characteristics and the use properties of macromolecule resin material (plastics, rubber).The softening agent that generally uses is mainly to be phthalic ester plasticizer at present, as dioctyl phthalate (DOP) (DOP), diethyl phthalate (DEP), dibutyl phthalate (DBP) etc.As the dioctyl phthalate (DOP) (DOP) of primary plasticizer by american cancer institute (NCI) suspect carcinogenesis is arranged after, use range is restricted.People are seeking and research, performance better surrogate more safer than DOP, and administrative authoritys such as external related food, makeup, medicine think that biomass class softening agent is a kind of bigger softening agent of security that can be used for the contact food package material.
At present, existing a considerable amount of the disclosing of vegetables oil nontoxic or low toxicity softening agent of utilizing for feedstock production.The patent No. is 200710020438.6, discloses " method for preparing epoxy plasticizer with sewer oil and waste oils and fats "; Wang Chunli etc. (" purposes of epoxy soybean oil and production method thereof ", " Shandong chemical industry ", 2006 the 35th volumes), Jiang Pingping (" technical Questions of Epoxidized Soybean and the application in PVC thereof ", " additives for plastics ", 2006 01 phases), Li Qing (" epoxy oleic acid monooctyl ester production technique ", " printing during chemical industry ", 2005 07 phases), Wang Yan (" synthesising process research of epoxy oil extracted from rice husks acid butyl ester ", " Liaodong College journal (natural science edition) ", 2005 04 phases, Ha Lidan buys and carries (" the hydrogen peroxide single stage method prepares epoxy oleum lini technology ", " chemistry world ",, the 10th phase in 2006) reported epoxy soybean oil, the epoxy Rice pollard oil, epoxy flax wet goods epoxidized vegetable oil is used for the plastic plasticizer of packaging material for food.Such softening agent has nontoxic, tasteless, and light and heat is had satisfactory stability, has the softening agent characteristics of thermo-stabilizer of holding concurrently.But there is the deficiency of following two aspects in such softening agent: 1. with vegetables oil as raw material, production cost is higher.2. such softening agent and plastics such as PVC (polyvinyl chloride) consistency is relatively poor, can only be used as the secondary softening agent of PVC and phthalic ester plasticizer such as DOP, and addition is limited, and general addition in PVC only is 1～5%.About being that the biofuel of main component is that the feedstock production chlorinated alkoxy biomass plasticizer does not see open with the fatty acid ester, thereby the present invention has remedied the deficiencies in the prior art.
Summary of the invention
The purpose of this invention is to provide that a kind of consistency is good, plasticization temperature is low, transport property is little, volatility is low, the preparation method of nontoxic, a kind of chlorinated alkoxy biomass plasticizer that production cost is low.
A kind of chlorinated alkoxy biomass plasticizer preparation method of the present invention, the technical scheme that is adopted may further comprise the steps:
(1) selecting iodine number for use is 50～120 biofuel, reactor adopts main reactor and the placed in-line method of auxiliary reactor (as Fig. 1), main reactor and auxiliary reactor are selected tank reactor or tower reactor for use, in main reactor and auxiliary reactor all by weight being biofuel: organic alcohol: catalyzer=100: 5～30: 0.05～0.2, biofuel, organic pure and mild catalyzer are added in main reactor and the auxiliary reactor, under the state that stirs, material is heated to 40～60 ℃, stops to heat stand-by; Described biofuel is to be the reproducibility fuel that stock oil is made by ester exchange process with natural phant oil plant and animal grease, food garbage oil, the iodine number of fatty acid ester degree of unsaturation is 50～120 in the described biofuel, described organic alcohol is the mixture of methyl alcohol, ethanol or methanol, and described catalyzer is one or more the composite use in ditertiary butyl peroxide, tert-butyl peroxide hydrogen, peroxidation benzene first two acyls, the azo-bis-isobutyl cyanide;
(2) open the liquid chlorine cylinder valve that calculates the weight, make liquid chlorine enter the chlorine vaporizer, chlorine through gasification and metering enters from the main reactor bottom, enter the chlorine of reactive system, fall 75% in the main reactor reaction consumes, remaining unreacted chlorine enters the bottom of auxiliary reactor, raw material in continuation and the auxiliary reactor reacts, because main reaction is thermopositive reaction, main reactor is provided with refrigerating unit, material in the reaction process in the main reactor is carried out necessary cooling, temperature of reaction is controlled in 50～100 ℃ of scopes, and auxiliary reactor is controlled at the balance of reaction heat that produces and the heat that distributes, temperature of reaction is controlled in 40～60 ℃ of scopes, and chlorine enters the speed control of reactive system at 40～60kg/h, and the logical chlorine time is reaction 2.5～4 hours, total logical chlorine dose is 20%～50% of a biofuel weight, stops logical chlorine;
(3) opening dry air system, the material in the main reactor is carried out depickling, is 0.5～1.2 hour 60～110 ℃ of depicklings, and depickling is finished;
(4) stablizer of adding biofuel weight 0.2%～0.4% obtains yellow transparent buttery product, carries out the blowing packing.
The preparation method of a kind of chlorinated alkoxy biomass plasticizer of the present invention, wherein by weight, biofuel: organic alcohol=100: 5～30 better are 100: 10～20, preferably 100: 15.
The preparation method of a kind of chlorinated alkoxy biomass plasticizer of the present invention, wherein the weight ratio of the chlorine of biofuel and liquid chlorine gasification is 100: 20～50, better is 100: 30～40, preferably 100: 35; The liquid chlorine vaporizing of the steel cylinder dress that the chlorine of described liquid chlorine gasification is commercially available and obtaining.
The preparation method of a kind of chlorinated alkoxy biomass plasticizer of the present invention, for making the more complete of chlorine reaction, adopt the method (as Fig. 1) of major and minor reactors in series, the temperature of reaction of main reactor is controlled at 50～100 ℃, better be 60～80 ℃, preferably 70 ℃.
The preparation method of a kind of chlorinated alkoxy biomass plasticizer of the present invention, the temperature of reaction of auxiliary reactor are controlled at 40～60 ℃, preferably 50 ℃.
The preparation method of a kind of chlorinated alkoxy biomass plasticizer of the present invention, the chlorine of chlorination reaction feeds speed control at 40～60kg/h.Better be 40～55kg/h., 50kg/h preferably.
The preparation method of a kind of chlorinated alkoxy biomass plasticizer of the present invention, it is 2.5～4 hours that the chlorine of chlorination reaction feeds reaction, better is 3～4 hours, preferably 3.5 hours.
The preparation method of a kind of chlorinated alkoxy biomass plasticizer of the present invention, described purification process is this area depickling purification process commonly used, specifically form: the air that at first reaction solution fed drying under 40～60 ℃ by following steps, heat up when feeding dry air, to reaction solution heating and remain on to 60～110 ℃, the time of depickling purifying is 0.5～1.2 hour, preferably 0.7～1.0 hour.
The preparation method of a kind of chlorinated alkoxy biomass plasticizer of the present invention, the stablizer of described interpolation, optional commercially available ethylene glycol diglycidylether, its addition are 0.2%～0.4% of biofuel weight, and optimum addition is 0.3% of a biofuel weight.
The preparation method of a kind of chlorinated alkoxy biomass plasticizer of the present invention, its catalyzer is one or more the composite use in ditertiary butyl peroxide, tert-butyl peroxide hydrogen, peroxidation benzene first two acyls, the azo-bis-isobutyl cyanide, its consumption is 0.05%～0.2% of a biofuel, better be 0.08%～0.15%, preferably 0.1%～0.15%.
Its advantage of the preparation method of a kind of chlorinated alkoxy biomass plasticizer of the present invention is that preparation process is simple, easy to control, with low cost, the chlorinated alkoxy biomass plasticizer product that is obtained has good consistency, replacement DOP that can vast scale joins in the PVC goods course of processing, adding proportion can be up to 50%, as plastic plasticizer, has the goods good-toughness, consistency is good, volatility is low, transport property is little, light and heat there are characteristics such as satisfactory stability effect, can be used for the food drink package material of contact, medical article material, the waterworks material, plastics such as toy for children; Can be used as the softening agent of plastics, rubber and the raw material of dispersion agent and environment-friendly type tensio-active agent etc. simultaneously.
Figure of description
Fig. 1 is preparation method's schema of the present invention.
Embodiment
Be elaborated below in conjunction with drawings and Examples:
It below is the non-limiting example of technical scheme of the present invention.
Embodiment 1:
Selecting iodine number for use is 85 biofuel.According to Fig. 1, major and minor reactor can be selected tank reactor for use, also can select tower reactor for use, is example with 1000 liters of tank reactors, in 1000 liters of major and minor lass lining stirred-tank reactors, all add biofuel 500kg, methyl alcohol 50kg, peroxidation benzene first two acyl catalyzer 0.5kg.Under stirring state, be warmed up to 55 ℃, stop to heat stand-by;
Open and be placed on liquid chlorine cylinder valve above the on-ground weigher, make liquid chlorine enter the chlorine vaporizer, enter from the main reactor bottom, enter the chlorine of reactive system, fall 70～80% in the main reactor reaction consumes, remaining unreacted Cl through the chlorine that gasifies and measure
2Enter the bottom of auxiliary reactor, the raw material in continuation and the auxiliary reactor reacts.Because this reaction is thermopositive reaction, main reactor should be provided with refrigerating unit, material in the reaction process in the main reactor is carried out necessary cooling, make temperature of reaction be controlled at 80 ℃, and auxiliary reactor remains essentially in the balance of reaction heat that produces and the heat that distributes, and temperature of reaction is 40 ℃;
Chlorine enters the speed control of reactive system at 50kg/h, and the logical chlorine time is 3 hours, and total logical chlorine dose is 150kg, and biofuel is 1: 0.33 with the weight ratio that feeds chlorine.Stop logical chlorine this moment, open dry air system, the material in the main reactor is carried out depickling, the refining time of depickling is 1 hour.After depickling was finished, the ethylene glycol diglycidylether stablizer of addition 2kg obtained yellow transparent buttery chloro methoxyl group biomass plasticizer product 605kg, carried out the blowing packing.The resulting chlorinated alkoxy biomass plasticizer performance index of the present invention see Table 1.
The resulting chlorinated alkoxy biomass plasticizer performance index of table 1 the present invention
Chlorinated alkoxy biomass plasticizer of the present invention relatively sees Table 2 with the addition of the plastics primary plasticizer dimixo-octyl phthalate of using always at present (DOP) to the PVC effect of material performance.
The addition of table 2 chlorinated alkoxy biomass plasticizer and DOP to the PVC effect of material performance relatively
Below be that table 2 is explained:
[1] with Shanghai altogether SG-63 (electric wire PP Pipe Compound) the PVC powder resin produced of enlightening Industrial Co., Ltd. be raw material, its benchmark is 100 fens resins, the umber that softening agent adds is 40 o'clock, the percentage that is equivalent to add softening agent is 80%.
[2] GB/T 5478-1985, plastic impact embrittlement temperature test method
[3] GB/T 1447-2005, the plastic tensile method for testing performance
Embodiment 2:
Selecting iodine number for use is 60 biofuel.According to Fig. 1, with 1000 liters of tank reactors is example, after embodiment 1 finishes, with the material in the auxiliary reactor of partial reaction, all be transported in the main reactor, iodine number is 60 biofuel 500kg, methyl alcohol 20kg, ethanol 20kg, liquid di-tert-butyl hydrogen peroxide 0.4kg in auxiliary reactor.Under stirring state, be warmed up to 40 ℃, stop to heat stand-by;
Open and be placed on liquid chlorine cylinder valve above the on-ground weigher, make liquid chlorine enter the chlorine vaporizer, enter the unreacted Cl of main reactor from the main reactor bottom through the chlorine that gasifies and measure
2Enter the bottom of auxiliary reactor, the raw material in continuation and the auxiliary reactor reacts.Material in the reaction process in the main reactor is carried out necessary cooling, make temperature of reaction be controlled at 50 ℃, the auxiliary reactor temperature of reaction is controlled at 40 ℃;
Chlorine enters the speed control of reactive system at 40kg/h, and the logical chlorine time is 3 hours, and total logical chlorine dose is 120kg, and biofuel is 100: 25 with the weight ratio that feeds chlorine.Stop logical chlorine this moment, open dry air system, the material in the main reactor is carried out depickling, the refining time of depickling is 1.2 hours.After depickling was finished, the ethylene glycol diglycidylether stablizer of addition 1.5kg obtained cl content and is 19.7% yellow transparent oily product 575kg.Carry out the blowing packing.
Embodiment 3:
Selecting iodine number for use is 95 biofuel.According to Fig. 1, be example with 1000 liters of tank reactors, after embodiment 2 finishes,, all be transported in the main reactor the material in the auxiliary reactor, iodine number is 95 biofuel 500kg, ethanol 75kg, azo-bis-isobutyl cyanide 0.4kg in auxiliary reactor.Under stirring state, be warmed up to 60 ℃, stop to heat stand-by;
Open the gageable liquid chlorine cylinder valve that is placed on above the on-ground weigher, after the liquid chlorine vaporization, enter the main reactor bottom, the unreacted Cl of main reactor
2Enter the bottom of auxiliary reactor, the raw material in continuation and the auxiliary reactor reacts.Material in the reaction process in the main reactor is carried out necessary cooling, make temperature of reaction be controlled at 70 ℃, the auxiliary reactor temperature of reaction is controlled at 50 ℃;
Chlorine enters the speed control of reactive system at 55kg/h, and the logical chlorine time is 3.5 hours, and total logical chlorine dose is 192.5kg, and biofuel is 100: 40 with the weight ratio that feeds chlorine.Stop logical chlorine this moment, open dry air system, the material in the main reactor is carried out depickling, the refining time of depickling is 1 hour.After depickling was finished, the ethylene glycol diglycidylether stablizer of addition 1.5kg obtained cl content and is 28.5% yellow transparent oily chloro oxyethyl group biomass plasticizer product 620kg, carried out the blowing packing.
Embodiment 4:
At 1000 liters of tank reactors, adding iodine number is 50 biofuel 500kg, methyl alcohol 15kg, liquid ditertiary butyl peroxide 0.25kg.Under stirring state, be warmed up to 60 ℃, stop to heat stand-by;
Open the gageable liquid chlorine cylinder valve that is placed on above the on-ground weigher, after the liquid chlorine vaporization, enter the main reactor bottom, the unreacted Cl of main reactor
2Enter the bottom of auxiliary reactor, the raw material in continuation and the auxiliary reactor reacts.Material in the reaction process in the main reactor is carried out necessary cooling, make temperature of reaction be controlled at 100 ℃, the auxiliary reactor temperature of reaction is controlled at 60 ℃;
Chlorine enters the speed control of reactive system at 40kg/h, and the logical chlorine time is 2.0 hours, and total logical chlorine dose is 80kg, and biofuel is 100: 20 with the weight ratio that feeds chlorine.Stop logical chlorine this moment, open dry air system, the material in the main reactor is carried out depickling, the refining time of depickling is 1 hour.After depickling was finished, the ethylene glycol diglycidylether stablizer of addition 1.0kg obtained cl content and is 15.5% yellow transparent oily product 567kg.Carry out the blowing packing.
Embodiment 5:
At 1000 liters of tank reactors, the adding iodine number is 120 biofuel 500kg, methyl alcohol 100kg, ethanol 50kg, peroxidation benzene first two acyl 1.0kg.Under stirring state, be warmed up to 40 ℃, stop to heat stand-by;
Open the gageable liquid chlorine cylinder valve that is placed on above the on-ground weigher, after the liquid chlorine vaporization, enter the main reactor bottom, the unreacted Cl of main reactor
2Enter the bottom of auxiliary reactor, the raw material in continuation and the auxiliary reactor reacts.Material in the reaction process in the main reactor is carried out necessary cooling, make temperature of reaction be controlled at 60 ℃, the auxiliary reactor temperature of reaction is controlled at 40 ℃;
Chlorine enters the speed control of reactive system at 60kg/h, and the logical chlorine time is 4.0 hours, and total logical chlorine dose is 240kg, and biofuel is 100: 50 with the weight ratio that feeds chlorine.Stop logical chlorine this moment, open dry air system, the material in the main reactor is carried out depickling, 100 ℃ of refining times of depickling are 0.8 hour.After depickling was finished, the ethylene glycol diglycidylether stablizer of addition 2.0kg obtained cl content and is 27.5% yellow transparent oily product 645kg.Carry out the blowing packing.
The above record only for using the embodiment of the technology of the present invention content, anyly is familiar with modification that this operator uses the present invention to do, variation, all belonged to the claim that the present invention advocates, and be not limited to cited embodiment.
Claims (4)
1. chlorinated alkoxy biomass plasticizer preparation method is characterized in that may further comprise the steps:
(1) selecting iodine number for use is 50～120 biofuel, reactor adopts main reactor and the placed in-line method of auxiliary reactor, main reactor and auxiliary reactor are selected tank reactor for use or are selected tower reactor for use, in main reactor and auxiliary reactor all by weight being biofuel: organic alcohol: catalyzer=100: 5～30: 0.05～0.2, biofuel, organic pure and mild catalyzer are added in main reactor and the auxiliary reactor, under the state that stirs, material is heated to 40～60 ℃, stops to heat stand-by; Described biofuel is to be the reproducibility fuel that stock oil is made by ester exchange process with natural phant oil plant and animal grease, food garbage oil, the iodine number of fatty acid ester degree of unsaturation is 50～120 in the described biofuel, described organic alcohol is the mixture of methyl alcohol, ethanol or methanol, and described catalyzer is a kind of in ditertiary butyl peroxide, the azo-bis-isobutyl cyanide;
(2) open the liquid chlorine cylinder valve that calculates the weight, make liquid chlorine enter the chlorine vaporizer, through gasification, the chlorine of metering enters from the main reactor bottom, the chlorine that enters reactive system falls 75% in the main reactor reaction consumes, remaining unreacted chlorine enters the bottom of auxiliary reactor, material in continuation and the auxiliary reactor reacts, be provided with refrigerating unit simultaneously and at main reactor, material in the reaction process in the main reactor is cooled off, temperature of reaction is controlled in 50～100 ℃ of scopes, and the auxiliary reactor temperature is controlled at the balance that reaction produces heat and distribute heat, temperature of reaction is controlled in 40～60 ℃ of scopes, and chlorine enters the speed control of reactive system at 40～60kg/h, and the logical chlorine time is reaction 2.5～4 hours, total logical chlorine dose is 20%～50% of a biofuel weight, stops logical chlorine;
(3) opening dry air system, the material in the main reactor is carried out depickling, is 0.5～1.2 hour 60～110 ℃ of depicklings, and depickling is finished;
(4) stablizer of adding biofuel weight 0.2%～0.4% obtains yellow transparent buttery product, carries out the blowing packing.
2. the preparation method of a kind of chlorinated alkoxy biomass plasticizer according to claim 1 is characterized in that the described chlorine of step (2) is formed by the vaporization of the liquid chlorine in the liquid chlorine steel.
3. the preparation method of a kind of chlorinated alkoxy biomass plasticizer according to claim 1, it is characterized in that the described depickling treating process of step (3), depickling is refining to be blown out reactant with dry air and realizes, dry air system is made up of air compressor, moisture eliminator and surge tank, temperature of charge in the reactor is at 60～110 ℃, and the depickling time is 0.5～1.2 hour.
4. the preparation method of a kind of chlorinated alkoxy biomass plasticizer according to claim 1 is characterized in that the described stablizer of step (4) is commercially available ethylene glycol diglycidylether, and addition is 0.3% of a biofuel weight.
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| CN103193637A (en) * | 2013-04-01 | 2013-07-10 | 福建致尚生物质材料发展有限公司 | Preparation method of bio-ester plasticizing agent |
| CN106046414B (en) * | 2016-07-13 | 2018-09-07 | 浙江赞宇科技股份有限公司 | A kind of method and device of continuous production biology base environmental protection flame retardant plasticizer |
| CN106946702A (en) * | 2017-04-14 | 2017-07-14 | 武汉轻工大学 | A kind of preparation method of chloromethoxy fatty acid methyl ester |
| CN111378289A (en) * | 2020-04-20 | 2020-07-07 | 山东岩海建设资源有限公司 | Chlorinated fatty acid ester environment-friendly plasticizer and preparation method thereof |
| CN111548720A (en) * | 2020-06-11 | 2020-08-18 | 三棵树涂料股份有限公司 | Bio-based single-component polyurethane waterproof coating and preparation method thereof |
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Application publication date: 20100512 Assignee: SHENZHEN ZHIBANG ELECTRONICS AND TECHNOLOGY CO., LTD. Assignor: Guangzhou University Contract record no.: 2014440020076 Denomination of invention: Method for preparing chlorinated alkoxy biomass plasticizer Granted publication date: 20110907 License type: Exclusive License Record date: 20140324 |
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