CN108047367A - Fluorine-contaninig polyacrylate dihydric alcohol and preparation method thereof - Google Patents

Fluorine-contaninig polyacrylate dihydric alcohol and preparation method thereof Download PDF

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CN108047367A
CN108047367A CN201711115290.4A CN201711115290A CN108047367A CN 108047367 A CN108047367 A CN 108047367A CN 201711115290 A CN201711115290 A CN 201711115290A CN 108047367 A CN108047367 A CN 108047367A
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fluorine
dihydric alcohol
contaninig polyacrylate
preparation
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CN108047367B (en
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王海波
杜晓声
杜宗良
成煦
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Sichuan University
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Sichuan University
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Abstract

Fluorine-contaninig polyacrylate dihydric alcohol of the present invention and preparation method thereof, chemical structure of general formula is as follows：

Description

Fluorine-contaninig polyacrylate dihydric alcohol and preparation method thereof
Technical field
The invention belongs to the synthesis technical fields of high molecular material polyalcohol, and in particular to fluorine-contaninig polyacrylate binary Alcohol and preparation method thereof.
Background technology
The electronegativity of fluorine atom is high, and polarizability is low, and with most strong oxidisability, fluorochemical is due to its special object Physicochemical property is widely used in the industries such as medicine, biology, chemical industry.Fluorinated dihydric alcohol is since the presence of terminal hydroxy group is often by as system The intermediate of standby high molecular material can prepare low surface property, water-fast solvent resistant, heat using Fluorinated dihydric alcohol as intermediate The high molecular material for the features such as stability is high, weatherability protrudes, such as elastomer, coating, plastics and foam etc..Esters of acrylic acid Polymer has excellent filming performance, chemical stability, thermal stability and inoxidizability, and derives from a wealth of sources.If there is one kind Fluorine-containing and polyacrylate is combined to the characteristic of fluorine element and acrylate polymer, is prepared into dihydric alcohol as high score The intermediate of sub- material is beneficial to exploitation multifunctional material.
Using free radical polymerisation process prepare polyacrylate polyol be a kind of relatively simple preparation method (such as specially A kind of drip-dry water soluble hydroxy acrylic resin of high solid and high light disclosed in sharp CN201610019259.X and its preparation side Method), and the polyacrylate polyol feed stock conversion prepared using this method is high, it is more that raw material variety may be selected, adjustment knot Structure is convenient, industrialized production easy to implement, but the hydroxyl in the polyalcohol prepared using free radical polymerisation process is located at strand Centre, the characteristics of due to Raolical polymerizable, quantity and position of the hydroxyl on molecule are also unable to control, and hydroxyl is system The chemical reaction functional group of standby polyurethane or polyester when it is used for the preparation of polyurethane or polyester as raw material, can make made Standby polyurethane or the molecular structure regularity and uniformity of polyester be not good enough, so as to materials such as prepared polyurethane and polyester Performance have very big influence.Similarly, the fluorine-contaninig polyacrylate dihydric alcohol prepared in this way is asked there is also identical Topic.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of hydroxyls to be located at the fluorine-containing poly- of strand both ends Acrylate dihydric alcohol and preparation method thereof, to meet the needs of polyurethane or polyester material preparation and be conducive to develop more work( It can high molecular material.
Fluorine-contaninig polyacrylate dihydric alcohol of the present invention, chemical structure of general formula are as follows：
Wherein, R1Base, R are remained to contain terminal hydroxy group azo initiator2And R4Structural formula be：
(note：R2And R4Two covalent bonds being located above in structural formula are main chain covalent bond, positioned at the covalent bond of bottom With branch R3Or R5Connection)
R3And R5For carbon number 1-20 containing fluoroalkyl or without fluoroalkyl, and R3And R5In at least one is former for carbon Subnumber 1-20's contains fluoroalkyl, R6Base is remained for mercaptoalcohol chain-transferring agent, n is number of repeat unit.The generally preferable scopes of n are 2-100.
Wherein, the azo initiator containing terminal hydroxy group remains based structures formula and is：
(note：Azo initiator containing terminal hydroxy group remains left end covalent bond in based structures formula and is connected with hydroxyl, right end and R2Connection)
Wherein, it is the hydroxyl alkyl that carbon number is 2-18 that mercaptoalcohol chain-transferring agent, which remains base,.
The preparation method of fluorine-contaninig polyacrylate dihydric alcohol of the present invention, raw material are：
Fluorinated acrylate monomer 85~99%
Terminal hydroxy group azo initiator 0.1~5%
Hydroxyl mercaptoalcohol chain-transferring agent 0.1~10%,
Raw material is：
Processing step is as follows：
(1) fluorinated acrylate monomer or fluorinated acrylate monomer and acrylate monomer are dissolved in shape in solvent A Into monomer solution, then add in hydroxyl mercaptoalcohol chain-transferring agent and terminal hydroxy group azo initiator into the monomer solution and mix When uniformly polymerisation 4~24 is small under 60~90 DEG C of stirring conditions, after the reaction time reaches, vacuum distillation is removed in reaction solution Solvent A, obtain intermediate polymer, the mass ratio of the solvent A and raw material total amount is (0.5~4)：1；
(2) intermediate polymer obtained by step (1) is added in solvent B and is uniformly mixed under stiring, then stand to It is few 24 it is small when, refilter removal solvent B and rinse gained filter cake with n-hexane, then by the filter cake after flushing at 40 ± 2 DEG C To get fluorine-contaninig polyacrylate dihydric alcohol when vacuum drying at least 20 is small, the mass ratio of the solvent B and intermediate polymer is (1 ~4)：1.
Wherein, the general structure of the fluorinated acrylate monomer is as follows：
In said structure general formula, R7For hydrogen-based or methyl, R8Contain fluoroalkyl for carbon number 1-20.Wherein, R8It is preferred that carbon Atom number is the fluorine-containing straight chained alkyl of 2-7.
Wherein, the general structure of the acrylate monomer is as follows：
In said structure general formula, R9For hydrogen-based or methyl, R10For the alkyl of carbon number 1-20.Wherein, R10It is preferred that carbon is former Sub- number is the straight chained alkyl of 2-7.
Wherein, the terminal hydroxy group azo initiator be 4,4'- azos double (4- cyano amylalcohols), 2,2'- azos (2- methyl- N- (2- hydroxyethyls) propionamide) or double (2- ethoxys) 2,2 '-azo-bis-isobutyrate.
Wherein, the general structure of the hydroxyl mercaptoalcohol chain-transferring agent is as follows：
HS-R11- OH
In said structure general formula, R11For the carbon number alkylidene of 2~18.In general, in order to reduce production cost, select It is easy to the raw material of purchase, usually selects R11For the carbon number straight-chain alkyl-sub of 2-5.
Wherein, the solvent A is tetrahydrofuran, ethyl acetate, butyl acetate, benzotrifluoride, dimethylformamide, two Methylacetamide or acetonitrile；The addition of solvent A is to play dissolution to raw material, and polymerization process is made to have preferable flowing Property.
Wherein, the solvent B is n-hexane, normal heptane, methanol or ethyl alcohol；Solvent B is used as precipitating reagent, will be poly- The resin for closing reaction generation precipitates separation in solvent B.
In step (2) finally selection with n-hexane rinse filter cake, be because n-hexane have the characteristics that dry it is volatile, It is and smaller using influencing for follow-up glycol products.
The invention has the advantages that：
1st, the hydroxyl of fluorine-contaninig polyacrylate dihydric alcohol of the present invention is located at strand both ends, and is primary hydroxyl knot Structure during intermediate feed as high molecular material, compared with the raw material of secondary hydroxyl structure, has relatively low steric effect, because And reactivity higher, reaction speed are faster, the conversion ratio of final reacting product also can higher so that for example poly- ammonia of sintetics The molecular structure of ester or polyester has more the regularity and uniformity of MOLECULE DESIGN requirement, so as to improve Polymer Synthesizing product Performance and quality.
2nd, the method for the invention introduces terminal hydroxy group using terminal hydroxy group azo initiator and hydroxyl mercaptoalcohol chain-transferring agent, So fluorine-contaninig polyacrylate dihydric alcohol molecular weight obtained is controllable, the carbon chain lengths between two hydroxyls are optional so that it is applied Field is extensive, has special construction and multi-functional material available for synthesis, such as synthesis has the fluorine-containing of surface super-hydrophobic Polymer.
3rd, preparation method of the present invention is easy to operate, and reaction is mild, is easy to control and isolates and purifies, raw material alternative is rich Richness, simplifies synthesis technology, and the conversion ratio of final product may be up to more than 96%.
Figure of description
Fig. 1 is the infrared spectrogram of fluorine-contaninig polyacrylate dihydric alcohol obtained by embodiment 1.
Fig. 2 not poly- ammonia of fluorine-containing aqueous obtained by fluorine-containing aqueous polyurethane film surface obtained by application examples 1 and comparative example 1 Ester film surface compares photo to the contact angle of water, wherein, fluorine-containing aqueous polyurethane is not thin obtained by comparative example 1 by left side WPU Film, the right WFPU are fluorine-containing aqueous polyurethane film obtained by application examples 1.
Specific embodiment
The explanation through a step done to the present invention below by specific embodiment, but the protection content of the present invention be not limited to Lower embodiment.
Embodiment 1
The processing step of the present embodiment is as follows：
(1) 178g ethyl acetate is weighed, 97.6g dodecafluoroheptyl methacrylates are added in reaction vessel and form methyl Dodecafluorhe-ptylacrylate solution, then by chain-transferring agent mercaprol 1.1g, azo initiator 4, double (the 4- cyano penta of 4'- azos Alcohol) 1.3g is added in reaction vessel and is uniformly mixed, 80 DEG C are then warming up to, under agitation polymerisation 15h.Reaction After time reaches, vacuum distillation removes ethyl acetate, obtains intermediate polymer；
(2) intermediate polymer obtained by step (1) is added in 300g n-hexanes and is uniformly mixed under stiring, in room temperature It is lower stand 24 it is small when, filtering removal n-hexane, then with n-hexane rinse filter cake, the filter cake after flushing is put into vacuum drying oven, It is -0.09MPa in vacuum degree, temperature is to be dried in vacuo 20h under 40 DEG C of environment, obtains fluorine-contaninig polyacrylate dihydric alcohol.It is made The conversion ratio of standby fluorine-contaninig polyacrylate dihydric alcohol is 97.5%.
Gained final product structure is characterized by infrared spectrogram, sees attached drawing 1.
It can be seen that by attached drawing 1：It is the characteristic absorption peak of hydroxyl at 3446cm-1, illustrates mercaprol and 4,4'- azos Hydroxyl has successfully been introduced into final product by double (4- cyano amylalcohols).The broad peak of 1000-1400cm-1 is that the vibration of C-F is inhaled Peak is received, is the characteristic absorption peak of ester carbonyl group at 1745cm-1.In addition, C=C absworption peaks disappear at 1645cm-1.By above-mentioned infrared Analysis result shows that gained final product fluorine-contaninig polyacrylate dihydric alcohol is the pure fluorine-containing polymethylacrylic acid ten of terminal hydroxy group Difluoro heptyl ester dihydric alcohol.
Embodiment 2
The processing step of the present embodiment is as follows：
(1) 50g tetrahydrofurans, 1g Hexafluorobutyl mathacrylates, 98g butyl acrylates is weighed to be added in reaction vessel Hexafluorobutyl mathacrylate and butyl acrylate mixed solution are formed, then chain-transferring agent mercaptoethanol 0.1g, terminal hydroxy group is even Nitrogen initiator 4, double (the 4- cyano amylalcohol) 0.1g of 4'- azos, which are added in reaction vessel, to be uniformly mixed, and is then warming up to 60 DEG C, Polymerisation is for 24 hours under stirring condition.After reaction time reaches, vacuum distillation removes ethyl acetate, obtains intermediate polymer；
(2) intermediate polymer obtained by step (1) is added in 120g n-hexanes and is uniformly mixed under stiring, in room temperature It is lower stand 24 it is small when, filtering removal n-hexane, then with n-hexane rinse filter cake, the filter cake after flushing is put into vacuum drying oven, It is -0.09MPa in vacuum degree, temperature is to be dried in vacuo 20h under 40 DEG C of environment, obtains fluorine-contaninig polyacrylate dihydric alcohol.
Embodiment 3
The processing step of the present embodiment is as follows：
(1) 400g dimethylformamides are weighed, 99g trifluoroethyl methacrylates are added in reaction vessel and form methyl Acrylic acid trifluoro ethyl ester solution, then by chain-transferring agent mercaptoethanol 0.4g, azo initiator 4,4'- azos are double (4- cyano amylalcohol) 0.6g is added in reaction vessel and is uniformly mixed, and is then warming up to 90 DEG C, under agitation polymerisation 4h.Reaction time arrives After reaching, vacuum distillation removes dimethylformamide, obtains intermediate polymer；
(2) intermediate polymer obtained by step (1) is added in 400g n-hexanes and is uniformly mixed under stiring, in room temperature It is lower stand 24 it is small when, filtering removal n-hexane, then with n-hexane rinse filter cake, the filter cake after flushing is put into vacuum drying oven, It is -0.09MPa in vacuum degree, temperature is to be dried in vacuo 20h under 40 DEG C of environment, obtains fluorine-contaninig polyacrylate dihydric alcohol.
Embodiment 4
The processing step of the present embodiment is as follows：
(1) 300g tetrahydrofurans, 50g dodecafluoroheptyl methacrylates and 50g methyl methacrylates is weighed to be added to Form dodecafluoroheptyl methacrylate and methyl methacrylate mixed solution in reaction vessel, then by chain-transferring agent sulfydryl second Alcohol 0.6g, azo initiator 4, double (the 4- cyano amylalcohol) 0.4g of 4'- azos, which are added in reaction vessel, to be uniformly mixed, and is then heated up To 80 DEG C, polymerisation 10h under agitation.After reaction time reaches, vacuum distillation removes tetrahydrofuran solvent, obtains intermediate Polymer；
(2) intermediate polymer obtained by step (1) is added in 200g n-hexanes and is uniformly mixed under stiring, in room temperature It is lower stand 24 it is small when, filtering removal n-hexane then rinses the filter cake with n-hexane, the filter cake after flushing is put into vacuum drying oven In, it is -0.09MPa in vacuum degree, temperature is to be dried in vacuo 20h under 40 DEG C of environment, obtains fluorine-contaninig polyacrylate dihydric alcohol.
Embodiment 5
The processing step of the present embodiment is as follows：
(1) 200g butyl acetates are weighed, 85g dodecafluoroheptyl methacrylates are added in reaction vessel and form methyl-prop Ten difluoro heptyl ester solution of olefin(e) acid, then by chain-transferring agent mercaprol 10g, azo initiator 4,4'- azos are double (4- cyano amylalcohol) 5g is added in reaction vessel and is uniformly mixed, and is then warming up to 65 DEG C, under agitation polymerisation 15h.Reaction time arrives After reaching, vacuum distillation removes ethyl acetate, obtains intermediate polymer；
(2) intermediate polymer obtained by step (1) is added in 300g n-hexanes and is uniformly mixed under stiring, in room temperature It is lower stand 24 it is small when, filtering removal n-hexane, then with n-hexane rinse filter cake, the filter cake after flushing is put into vacuum drying oven, It is -0.09MPa in vacuum degree, temperature is to be dried in vacuo 20h under 40 DEG C of environment, obtains fluorine-contaninig polyacrylate dihydric alcohol.
Application examples 1
Embodiment 1 is prepared into the fluorine-containing ten difluoro heptyl ester dihydric alcohol 0.9554g of polymethacrylates of gained terminal hydroxy group, diformazan It is uniformly mixed after phenylene diisocyanate 15g, polypropylene glycol 20.36g and dihydromethyl propionic acid 2.25g vacuum dehydrations, at 85 DEG C 3h is reacted, after the reaction time reaches, adds in chain extender 1,4-butanediol 1.84g, reaction extremely-NCO reaches theoretical value at 70 DEG C, Reaction product is cooled to 35 DEG C, triethylamine 1.70g stirrings is added in and neutralizes 30min, finally add in deionization under high velocity agitation Water carries out emulsion dispersion chain extension, obtains fluorine-containing aqueous polyurethane lotion, then fluorine-containing aqueous polyurethane lotion is prepared as fluorine-containing aqueous Polyurethane film.
Comparative example 1
With reference to 1 method of application examples, difference part is fluorine-containing ten difluoro heptyl ester dihydric alcohol equivalent of polymethacrylates Polypropylene glycol is replaced with, not fluorine-containing waterborne polyurethane film is finally made, carries out the contact angle test to water, test result respectively As shown in Figure 2.
It can see from the comparing result of attached drawing 2, even if adding in minimal amount in Raw Materials for Waterborne Polyurethane formula by implementing Example 1 be made fluorine-contaninig polyacrylate dihydric alcohol just can by synthesized fluorine-containing aqueous polyurethane film surface to the contact angle of water from 60 ° are increased to 108 °, substantially increase the hydrophobic performance of aqueous polyurethane, have reached and have reduced fluorine-containing raw material dosage and energy to the greatest extent Significantly improve the purpose of polymer hydrophobic performance.

Claims (10)

1. fluorine-contaninig polyacrylate dihydric alcohol, it is characterised in that chemical structure of general formula is as follows：
Wherein, R1Base, R are remained to contain terminal hydroxy group azo initiator2And R4Structural formula be：
R3And R5For carbon number 1-20 containing fluoroalkyl or without fluoroalkyl, and R3、R5In at least one be carbon number 1- 20 containing fluoroalkyl, R6Base is remained for mercaptoalcohol chain-transferring agent, n is number of repeat unit.
2. fluorine-contaninig polyacrylate dihydric alcohol according to claim 1, it is characterised in that：N is 2~100.
3. fluorine-contaninig polyacrylate dihydric alcohol according to claim 1 or claim 2, it is characterised in that：The azo containing terminal hydroxy group draws Hair agent remains based structures formula and is：
4. fluorine-contaninig polyacrylate dihydric alcohol according to claim 1 or claim 2, it is characterised in that：Mercaptoalcohol chain-transferring agent remains base For the hydroxyl alkyl of carbon number 2-18.
5. the preparation method of fluorine-contaninig polyacrylate dihydric alcohol described in a kind of claim 1, it is characterised in that raw material is：
Fluorinated acrylate monomer 85~99%
Terminal hydroxy group azo initiator 0.1~5%
Hydroxyl mercaptoalcohol chain-transferring agent 0.1~10%,
Raw material is：
Processing step is as follows：
(1) fluorinated acrylate monomer or fluorinated acrylate monomer and acrylate monomer are dissolved in solvent A and form list Liquid solution, then add in hydroxyl mercaptoalcohol chain-transferring agent and terminal hydroxy group azo initiator into the monomer solution and be uniformly mixed When polymerisation 4~24 is small under 60~90 DEG C of stirring conditions, after the reaction time reaches, vacuum distillation removes molten in reaction solution Agent A, obtains intermediate polymer, and the mass ratio of the solvent A and raw material total amount is (0.5~4)：1；
(2) intermediate polymer obtained by step (1) is added in solvent B and is uniformly mixed under stiring, then stand at least 24 Hour, it refilters removal solvent B and rinses gained filter cake with n-hexane, then by the filter cake after flushing in 40 ± 2 DEG C of vacuum It is dry at least 20 it is small when to get fluorine-contaninig polyacrylate dihydric alcohol, the mass ratio of the solvent B and intermediate polymer for (1~ 4)：1.
6. the preparation method of fluorine-contaninig polyacrylate dihydric alcohol according to claim 5, it is characterised in that：The fluorine-containing propene The general structure of acid ester monomer is as follows：
In said structure general formula, R7For hydrogen-based or methyl, R8Contain fluoroalkyl for carbon number 1-20；
The general structure of the acrylate monomer is as follows：
In said structure general formula, R9For hydrogen-based or methyl, R10For the alkyl of carbon number 1-20.
7. the preparation method of fluorine-contaninig polyacrylate dihydric alcohol according to claim 6, it is characterised in that：R8For carbon number 2-7's contains fluoroalkyl, R10For the alkyl of carbon number 2-7.
8. according to the preparation method of the fluorine-contaninig polyacrylate dihydric alcohol of claim 5 or 6, it is characterised in that：The end hydroxyl Base azo initiator is 4,4'- azos double (4- cyano amylalcohol), 2,2'- azos (2- methyl-N- (2- hydroxyethyls) propionamide) Or double (2- ethoxys) 2,2 '-azo-bis-isobutyrate；
The general structure of the hydroxyl mercaptoalcohol chain-transferring agent is as follows：
HS-R11- OH
In said structure general formula, R11For the carbon number alkylidene of 2~18.
9. the preparation method of fluorine-contaninig polyacrylate dihydric alcohol according to claim 8, it is characterised in that：R11For carbon number The alkylidene of 2-5.
10. according to the preparation method of the fluorine-contaninig polyacrylate dihydric alcohol of claim 5 or 6, it is characterised in that：Described is molten Agent A is tetrahydrofuran, ethyl acetate, butyl acetate, benzotrifluoride, dimethylformamide, dimethyl acetamide or acetonitrile；It is described Solvent B be n-hexane, normal heptane, methanol or ethyl alcohol.
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