CN103113565B - Preparation method and new application of polyethyleneglycol-maleic anhydride polycondensate and antistatic finishing agent prepared from polyethyleneglycol-maleic anhydride polycondensate - Google Patents
Preparation method and new application of polyethyleneglycol-maleic anhydride polycondensate and antistatic finishing agent prepared from polyethyleneglycol-maleic anhydride polycondensate Download PDFInfo
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- CN103113565B CN103113565B CN201310058997.1A CN201310058997A CN103113565B CN 103113565 B CN103113565 B CN 103113565B CN 201310058997 A CN201310058997 A CN 201310058997A CN 103113565 B CN103113565 B CN 103113565B
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Abstract
The invention discloses a preparation method of polyethyleneglycol-maleic anhydride polycondensate. The polyethyleneglycol-maleic anhydride polycondensate is prepared through condensation polymerization of polyethyleneglycol with the molecular weight of 400-2000 and the maleic anhydride at different system atmospheres and temperatures. The preparation method disclosed by the invention is simple in technology and easy to control, and can be used for effectively preventing the phenomenon that crosslinking and solidification gelatination occur in a reaction process of the polyethyleneglycol-maleic anhydride polycondensate, and the prepared product has light color. The invention also discloses an application of the olyethyleneglycol-maleic anhydride polycondensate serving as an antistatic agent and an antistatic finishing agent prepared from the polyethyleneglycol-maleic anhydride polycondensate. The antistatic finishing agent is used for antistatic finish of fiber fabrics, can be used for obviously reducing the voltage of electrification by friction of the fiber fabrics and endowing the fiber fabrics with a durable antistatic effect.
Description
Technical field
The present invention relates to high molecular polymer technical field, especially relate to a kind of preparation method and Xin purposes of polycondensate.
Background technology
As everyone knows, synthon or high by the fabric face resistivity of its making, belong to high-insulativity material, and high-insulativity brings the problem of static hazard to fabric.Because fabric friction easily occurs and accumulate static charge in goods processing or final use procedure, this causes fabric easily to adsorb dust; While wearing, because discharging, make people produce sticky feeling; In clean room, electric discharge also can cause series harm, as punctures electronic devices and components, causes short circuit to burn out.For the harm that prevents that static charge accumulation from bringing, people have taked a series of measure, for example, utilize polymer permanent antistatic agent to carry out rear arrangement to fabric, reduce the surface resistivity of fabric, fabric are obtained persistent antistatic.The polymeric antistatic agent that fiber finishing is conventional has polyester polyether-type, polyacrylate, polyurethane-type etc., but these static inhibitor are Shortcomings part all, as polyester polyether-type static inhibitor synthesis technique is difficult, control, hydrophilic segment is too much, and washing fastness is not good; Polyacrylate static inhibitor has the quaternary ammonium salt of antistatic effect, and antistatic effect is good, but in order to improve washing fastness, need to carry out crosslinking Treatment to resin, and the amount of adding during this class static inhibitor is larger, and cost is higher; Static inhibitor the use of polyurethane-type static inhibitor needs and other types, could obtain good effect, and this also makes cost increase.
Unsaturated polyester is generally the chain macromolecule compound with ester bond and unsaturated double-bond being formed by unsaturated dibasic acid and dibasic alcohol or monounsaturated dicarboxylic acid and unsaturated dibasic alcohol polycondensation.Due to raw materials used difference, kind is also various.Mono-esterification, double esterification or the polycondensation product that polyoxyethylene glycol and maleic anhydride make as raw material of wherein take is a kind of high performance water reducer.But the polycondensation product of polyoxyethylene glycol and maleic anhydride is many unsaturated double-bonds because molecular chain has, under vacuum high-temperature, easily occur during polymerization crosslinked, tending to cause reacting the later stage there is curing gel, the darken phenomenon of even blackening of product, and this has limited its application.
Summary of the invention
For the defect of polyoxyethylene glycol-maleic anhydride polycondensate preparation method existence in prior art, the invention provides a kind of preparation method of polyoxyethylene glycol-maleic anhydride polycondensate.For achieving the above object, the technical scheme that the present invention takes is: a kind of preparation method of polyoxyethylene glycol-maleic anhydride polycondensate, and under catalyzer exists, there is polycondensation in polyoxyethylene glycol and maleic anhydride, and reaction comprises the following steps:
(1) polyoxyethylene glycol and maleic anhydride are reacted 1～5 hour under catalyzer, nitrogen atmosphere, 70～100 ℃ of conditions;
(2) then the intermediate product of step (1) is reacted 1～2 hour under nitrogen atmosphere, 150～160 ℃ of conditions;
(3) intermediate product of step (2) is reacted under vacuum state, 170～180 ℃ of conditions to acid number be 30～50mgKOH/g, preferred reaction to acid number is 35～40mgKOH/g.
Described molecular weight polyethylene glycol is 400～2000.
The mol ratio of described polyoxyethylene glycol and maleic anhydride is 1: 1.05 to 1: 1.25.
The mass percent that described catalyzer accounts for the total material of reaction is 0.5～2%.
Described catalyzer is the acid compounds that is selected from tosic acid, heteropolyacid, Weibull, sulfuric acid, or is selected from the aminated compounds of triethyl ammonium, tetramethylammonium bromide, Trimethyllaurylammonium bromide.
In described step (1) or add stopper in step (1) and step (3) respectively.
In above-mentioned reaction, add stopper can prevent that the bad phenomenon of curing gel from appearring in reaction process and reaction product while storing, except adding stopper in step (1), also can in step (1) and step (3), add stopper respectively, add in two steps and can to a certain degree suppress stopper and consumed in a large number because of pyrolytic decomposition in step (3), thereby reduce total consumption of stopper.
The mass percent of the total material of the shared reaction of described stopper is 0.02～0.1%.
Described stopper is the phenolic compound that is selected from Resorcinol, methyl hydroquinone, p-ten.-butylcatechol, tert-butyl catechol.
In order to overcome the defects such as existing polymeric antistatic agent antistatic effect is not good and not washable, the present invention also provides the antistatic finishing agent for textile finishing of a kind of new static inhibitor and preparation thereof.
The present invention adopts polyoxyethylene glycol-maleic anhydride polycondensate prepared by aforesaid method as static inhibitor.
An antistatic finishing agent, comprises polyoxyethylene glycol-maleic anhydride polycondensate, initiator and thinner prepared by aforesaid method.
Described initiator is azo-compound or organo-peroxide.
Described azo-compound is one or more of Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), azo isobutyl cyano group methane amide.
Described organo-peroxide be di-t-butyl peroxide, dicumyl peroxide, peroxidation decoyl, lauroyl peroxide, peroxide acetic acid butyl ester, the peroxidation lauric acid tert-butyl ester one or more.
Described initiator amount is 0.5%～2% of polyoxyethylene glycol-maleic anhydride polycondensate quality.
The organic solvent that described thinner selects pure water, can dissolve each other with water or above both mixed solvent.
The described organic solvent that can dissolve each other with water refers to ethanol, ethylene glycol, Virahol or glycerol etc.
In described antistatic finishing agent, the content of polyoxyethylene glycol-maleic anhydride polycondensate is 40g/L～80g/L.
By the antistatic finishing agent making by padding, the method such as coating carries out after antistatic finish synthetic fiber fabrics such as acrylic fibers, terylene, polyamide fibres, at 100～180 ℃, cures, according to selected stoving temperature, the time of curing is between 5～10min.
The preparation method of polyoxyethylene glycol-maleic anhydride polycondensate provided by the present invention, technique is simple and easy to control; Because having prevented polycondensation product effectively, the intermediate reaction process of step (2) under nitrogen atmosphere, 150～160 ℃ of conditions in preparation process, there is the crosslinked phenomenon that occurs curing gel, and the product making is of light color, for the treatment of fabric, there will not be the phenomenon of " dyeing ".The present invention has creatively found the new purposes of polyoxyethylene glycol-maleic anhydride polycondensate in static inhibitor field, the fabric arranging with antistatic finishing agent prepared by this polycondensation product, resistance and triboelectrification voltage significantly reduce, washing fastness is good, through repeatedly washing, the triboelectrification voltage of fabric still can meet service requirements.And static inhibitor provided by the present invention without with other static inhibitor use, cost is lower.
Embodiment
Below in conjunction with embodiment, the present invention is further described.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
In the present invention, the triboelectrification voltage test method of fabric is as follows:
Adopt anti-electrostatic industry conventional " triboelectrification voltage test method " to measure the triboelectrification voltage of fabric, test procedure is as follows:
(1) sample fixedly lies on testing stand;
(2) with pure cotton cloth, make abrasive material, bestow the pressure of sample 10N;
(3) with abrasive material on sample with the unidirectional friction of speed of 1 time per second 20 times;
(4) after having rubbed, rapidly the probe of electrostatic tester is slided along friction track, probe is 10～20mm with the distance of sample;
(5) peak voltage recording is the triboelectrification voltage of this sample.
The surface resistivity testing method of fabric is with reference to < < GB12014-2009 antistatic clothing > >.
Embodiment 1:
In embodiment 1, the mol ratio of polyoxyethylene glycol and maleic anhydride is 1: 1.05, the mass percent that catalyst levels accounts for the total material of reaction is 0.5%, stopper adds in step (1), the mass percent that stopper consumption accounts for the total material of reaction is 0.03%, molecular weight polyethylene glycol is 400, and state is liquid.Preparation process is as follows:
(1) in reactor, add 100g (0.25mol) polyoxyethylene glycol (Mw=400), 25.73g maleic anhydride, 0.63g tosic acid, 0.04g Resorcinol, pass into nitrogen and exclude after the air in reactor, reaction mixture stirring reaction 2 hours at 100 ℃ of temperature;
(2) temperature is slowly risen to 160 ℃, temperature-rise period completes within half hour, and at this temperature, continues reaction 1.5h;
(3) stop logical nitrogen, guarantee the stopping property of reactor, and reactor is vacuumized, temperature rises to 180 ℃, react to acid number be 30mgKOH/g, stop heating, reaction product is cooled to room temperature, obtain light yellow viscous liquid.
Embodiment 2:
In embodiment 2, except stopper, the quality of unclassified stores is identical with embodiment 1, and stopper adds respectively in step (1) and step (3), and it is 0.02% that the total consumption of stopper accounts for the total material per-cent of reaction.Preparation process is as follows:
(1) in reactor, add 100g (0.25mol) polyoxyethylene glycol (Mw=400), 25.73g maleic anhydride, 0.63g tosic acid, 0.02g Resorcinol, pass into nitrogen and exclude after the air in reactor, reaction mixture stirring reaction 2 hours at 100 ℃ of temperature;
(2) temperature is slowly risen to 160 ℃, temperature-rise period completes within half hour, and at this temperature, continues reaction 1.5h;
(3) stop logical nitrogen, guarantee the stopping property of reactor, and reactor is vacuumized, temperature rises to 180 ℃, react to acid number be 35mgKOH/g, stop heating, reaction product is cooled to 45 ℃, add 0.01g Resorcinol, then be cooled to room temperature, obtain light yellow viscous liquid.
Embodiment 3:
In embodiment 3, the mol ratio of polyoxyethylene glycol and maleic anhydride is 1: 1.10, the mass percent that catalyst levels accounts for total reaction material is 1%, stopper adds respectively in step (1) and step (3), the mass percent that total consumption accounts for total reaction material is 0.05%, molecular weight polyethylene glycol is 1000, state is solid-state, and fusing point is 37 ± 2 ℃.Preparation process is as follows:
(1) in reactor, add 200g (0.20mol) polyoxyethylene glycol (Mw=1000), 21.56g maleic anhydride, be warming up to 40 ℃, be stirred to after the whole fusings of polyoxyethylene glycol, add 0.21g triethyl ammonium, 0.09g methyl hydroquinone, pass into nitrogen and exclude after the air in reactor, reaction mixture stirring reaction 3 hours at 85 ℃ of temperature;
(2) temperature is slowly risen to 150 ℃, temperature-rise period completed in 40 minutes, and at this temperature, continued reaction 1h;
(3) stop logical nitrogen, guarantee the stopping property of reactor, and reactor is vacuumized, temperature rises to 170 ℃, react to acid number be 40mgKOH/g, stop heating, reaction product is cooled to 50 ℃, add 0.02g methyl hydroquinone, then be cooled to room temperature, obtain light yellow viscous liquid.
Embodiment 4:
In embodiment 4, the mol ratio of polyoxyethylene glycol and maleic anhydride is 1: 1.25, the mass percent that catalyst levels accounts for total reaction material is 2%, stopper adds respectively in step (1) and step (3), the mass percent that total consumption accounts for reaction mass is 0.1%, molecular weight polyethylene glycol is 2000, state is solid-state, and fusing point is 51 ± 2 ℃.Preparation process is as follows:
(1) in reactor, add 400g (0.20mol) polyoxyethylene glycol (Mw=2000), 24.5g maleic anhydride, be warming up to 55 ℃, be stirred to after the whole fusings of polyoxyethylene glycol, add 0.85g tetramethylammonium bromide, 0.28g tert-butyl catechol, pass into nitrogen and exclude after the air in reactor, be warming up to stirring reaction 5h at 70 ℃;
(2) temperature is slowly risen to 150 ℃, temperature-rise period completed in 30 minutes, and at this temperature, continued reaction 2h;
(3) stop logical nitrogen, guarantee the stopping property of reactor, and reactor is vacuumized, temperature rises to 180 ℃, react to acid number be 50mgKOH/g, stop heating, reaction product is cooled to 50 ℃, add 0.14g tert-butyl catechol, then reaction product is cooled to room temperature, obtain light yellow viscous liquid.
Except the catalyst type that above embodiment enumerates, for the preparation of the catalyzer of polyoxyethylene glycol-maleic anhydride polycondensate of the present invention, can also be heteropolyacid, Weibull, sulfuric acid, Trimethyllaurylammonium bromide etc.
Embodiment 5-7:
Embodiment 5-7 is the antistatic finishing agent of selecting the prepared static inhibitor composition of embodiment 1 to prepare by table 1 component and component concentration, with this finishing composition, adopt the method for padding not carry out antistatic finish to making the polyester fabric of any antistatic finish, dry solidification 7min at 140 ℃, then surveys its surface resistivity and triboelectrification voltage.
Comparative example 1: the fabric dry 7min at 140 ℃ that does not do any antistatic finish.
Table 1 fabric antistatic finish result
The initiator that embodiment 5 selects is Diisopropyl azodicarboxylate, and the initiator that embodiment 6 selects is 2,2'-Azobis(2,4-dimethylvaleronitrile), and the initiator that embodiment 7 selects is azo isobutyl cyano group methane amide.As can be seen from the table, fabric surface resistivity and Abrasive voltage after arranging with the prepared antistatic finishing agent of the embodiment of the present invention all obviously decline, and antistatic effect is better, after 30 washings, the triboelectrification voltage of fabric is still lower than 100V, and washing fastness is good.Static inhibitor content is larger, and antistatic effect is better.
Embodiment 8-10:
Embodiment 8-10 is the antistatic finishing agent of preparing by table 2 component and component concentration, and wherein embodiment 8 and 9 selects the prepared product of embodiment 3 as static inhibitor, and embodiment 10 selects the prepared product of embodiment 4 as static inhibitor.With this finishing composition, adopt the method for padding not carry out antistatic finish to making the acrylic fabric of any antistatic finish, dry solidification 5min at 180 ℃, then surveys its surface resistivity and triboelectrification voltage.
Comparative example 2: do not make the fabric of any antistatic finish at 180 ℃ of dry 5min
Table 2 fabric antistatic finish result
The initiator that embodiment 8 selects is dicumyl peroxide, and the initiator of embodiment 9 is peroxidation decoyl, and the initiator of embodiment 10 is peroxide acetic acid butyl ester.Select as seen from Table 2 antistatic finishing agent prepared by dissimilar peroxide initiator can obtain the also reduction greatly of desirable antistatic effect, Abrasive voltage, and the triboelectrification magnitude of voltage of washing after 30 times is still lower.
Peroxide initiator can also be selected di-t-butyl peroxide, lauroyl peroxide, the peroxidation lauric acid tert-butyl ester etc., can obtain effect of the present invention equally.
Claims (9)
1. a preparation method for polyoxyethylene glycol-maleic anhydride polycondensate, is characterized in that, polyoxyethylene glycol and maleic anhydride, under catalyzer exists, polycondensation occurs, and reaction comprises the following steps:
(1) polyoxyethylene glycol and maleic anhydride are reacted 1～5 hour under catalyzer, nitrogen atmosphere, 70～100 ℃ of conditions;
(2) then the intermediate product of step (1) is reacted 1～2 hour under nitrogen atmosphere, 150～160 ℃ of conditions;
(3) intermediate product of step (2) is reacted under vacuum state, 170～180 ℃ of conditions to acid number be 30～50mgKOH/g;
Described molecular weight polyethylene glycol is 400～2000; The mol ratio of described polyoxyethylene glycol and maleic anhydride is 1:1.05 to 1:1.25; Described catalyzer is the acid compounds that is selected from tosic acid, heteropolyacid, Weibull, sulfuric acid, or is selected from the aminated compounds of triethyl ammonium, tetramethylammonium bromide, Trimethyllaurylammonium bromide.
2. the preparation method of a kind of polyoxyethylene glycol-maleic anhydride polycondensate according to claim 1, is characterized in that, step (3) under vacuum state, 170～180 ℃ of conditions, react to acid number be 35～40mgKOH/g.
3. the preparation method of a kind of polyoxyethylene glycol-maleic anhydride polycondensate according to claim 1, is characterized in that, in described step (1) or add stopper in step (1) and step (3) respectively.
4. the preparation method of a kind of polyoxyethylene glycol-maleic anhydride polycondensate according to claim 3, is characterized in that described stopper is the phenolic compound that is selected from Resorcinol, methyl hydroquinone, p-ten.-butylcatechol, tert-butyl catechol.
5. polyoxyethylene glycol-maleic anhydride polycondensate that as described in claim 1-4 any one prepared by method is as the purposes of static inhibitor.
6. an antistatic finishing agent, is characterized in that, comprises polyoxyethylene glycol-maleic anhydride polycondensate, initiator and thinner that as described in claim 1-4 any one prepared by method.
7. a kind of antistatic finishing agent according to claim 6, is characterized in that, described initiator is azo-compound or organo-peroxide.
8. a kind of antistatic finishing agent according to claim 7, is characterized in that, described azo-compound is one or more of Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), azo isobutyl cyano group methane amide.
9. a kind of antistatic finishing agent according to claim 7, it is characterized in that, described organo-peroxide is one or more of di-t-butyl peroxide, dicumyl peroxide, peroxidation decoyl, lauroyl peroxide, peroxide acetic acid butyl ester, the peroxidation lauric acid tert-butyl ester.
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| CN201310058997.1A CN103113565B (en) | 2013-02-25 | 2013-02-25 | Preparation method and new application of polyethyleneglycol-maleic anhydride polycondensate and antistatic finishing agent prepared from polyethyleneglycol-maleic anhydride polycondensate |
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