CN103910833B - Organosilicon modified fluorine-containing polyacrylate waterproof oil resistant emulsion and preparation method thereof - Google Patents
Organosilicon modified fluorine-containing polyacrylate waterproof oil resistant emulsion and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an organosilicon modified fluorine-containing polyacrylate waterproof oil resistant emulsion and a preparation method thereof, which belongs to the emulsion production field. The emulsion is prepared by an organosilicon monomer, an emulsifier, a catalyst, a monomer A, a monomer B, sodium hyposulfite, an initiator and water with specific ratio. Compared with prior art, the organosilicon modified fluorine-containing polyacrylate waterproof oil resistant emulsion has better waterproof oil resistant performance, has simple production technology, and has good popularization and application value.
Description
Technical field
The present invention relates to emulsion preparation field, specifically a kind of organic-silicon-modified fluorine-contaninig polyacrylate waterproof and oilproof
Emulsion and preparation method thereof.
Background technology
China's paper-making industry grew continuously and fast from nineteen ninety, had nowadays become the paper industry big country in the world the 2nd, production equipment
Also rank world's first.Progress with the epoch and the reinforcement of people's environmental consciousness, paper products gradually instead of many difficult falls
The plastic of solution, is widely used for food and drink, food, confection etc. and daily life in terms of packaging.It is applied to packaging side
The paper products in face will have certain Water-proof and oil-proof function, can apply the continuously fine and close inclusion poly- third of last layer on the surface of paper
The high-molecular organic materials such as olefin(e) acid ester, polyethylene, polyvinyl alcohol, carboxymethyl cellulose, but this kind of macromolecular material is difficult in itself
Degraded, can bring harm to environment.It is also that paper is carried out with Lasaxing Oilfield, aluminium powder coating and aluminium foil lamination, but these materials are originally
Body also not oil resistant.Developed country's commonly used fluorine carbon waterproof and oilproof auxiliary agent from the 1950's passes through interpolation, table in slurry
The method of face applying glue or coating process to carry out surface modification to paper pulp fiber, using formed fluorocarbon surfactant coating because
Fluorocarbon chain arranges outwardly and has low surface energy to reach the purpose making paper have waterproof and oilproof performance.Prevent through fluorine carbon waterproof
The paper surface that oil preparation was processed is difficult by the vegetable oil of aqueous substance and majority, animal oil, mineral oil, the moistening of solvent institute,
But it is as the requirement more and more higher to waterproof and oilproof for the social progress, fluorine carbon water and oil repellent agent can not expire for high request
Foot.
, because of its excellent film property, good gloss retention and remarkable mechanical performance are in coating row for polyacrylate emulsion
Industry is used widely, but polyacrylic acid ester molecule is linear structure, lacks crosslinking points, and because side base is hydrophilic polar group
Group, coating has certain water penetration, and especially when by sunlight, wind and rain, acidic materials effect, ester bond is susceptible to hydrolyze,
Film performance is made to decline.The patent documentation of Publication No. cn102911308a discloses a kind of fluorine-contaninig polyacrylate/bis-
Sized nanostructures sio2The preparation method of complex emulsions, this technology by the way of inorganic material silicon dioxide with fluorine-containing polyacrylic acid
Ester carries out compound reaction although overcoming above-mentioned deficiency, but needs to prepare the nanometer titanium dioxide of two kinds of particle diameters in synthetic reaction
Silicon grain, technique more complicated it is difficult to realize large-scale promotion application.
Content of the invention
The technical assignment of the present invention is for above-mentioned the deficiencies in the prior art, provides a kind of organic-silicon-modified fluorine-containing polypropylene
Acid esters waterproof and oilproof emulsion.
The further technical assignment of the present invention is the preparation method providing above-mentioned emulsion.
The technical assignment of the present invention is realized in the following manner: a kind of organic-silicon-modified fluorine-contaninig polyacrylate waterproof is prevented
Fat liquor, is obtained by the raw material of following weight proportion:
Organic silicon monomer 5-8 part；
Emulsifying agent 0.5-0.7 part；
Catalyst 0.1-0.3 part；
Monomer one 20-40 part；
Monomer two 3-5 part；
Sodium thiosulfate 0.4-0.6 part；
Initiator 0.2-0.4 part；
65 parts of water；
Preparation method comprises the following steps:
(1) organic silicon monomer, emulsifying agent, water and the catalyst of metering are added in reaction vessel, high-speed stirred is to abundant
Pre-emulsification；
(2) after pre-emulsification, it is warmed up to 80～85 DEG C, make organic silicon monomer carry out ring-opening polymerization and (generate linearly poly silicon
Oxygen alkane is conducive to reaction below), maintain 2～3h, then cool to 40-60 DEG C, Deca monomer one, monomer two, place one section
It is swelling that time makes monomer one, monomer two that organic silicon seed (i.e. linear polysiloxane) is carried out；
(3) it is warmed up to 70～80 DEG C, is initially charged sodium thiosulfate, add initiator, emulsion moment has milky to be changed into
Translucent light blue, after to be triggered dose adds, react 1-4h, make monomer one, monomer two and organic silicon monomer reaction fully, that is,
Obtain organic-silicon-modified fluorinated acrylate waterproof and oilproof emulsion.
Described organic silicon monomer is preferably octamethylcy-clotetrasiloxane (d4) and/or vinyl triethoxyl siloxanes (a-
151).
Described emulsifying agent is preferably sodium lauryl sulphate (sds) and/or octyl phenol polyoxyethylene ether -10(op-
10).
Described catalyst is preferably potassium peroxydisulfate or sodium peroxydisulfate.
Described monomer one is preferably the mixture of methyl methacrylate and butyl acrylate, methyl methacrylate and third
The mass ratio of olefin(e) acid butyl ester is 1/1.5～1.5/1.
Monomer two is preferably Hexafluorobutyl mathacrylate.
Above-mentioned monomer one, monomer two all play the effect of Water-proof and oil-proof and film forming, and its point is classified as monomer one, monomer two
Merely for convenience its consumption is defined.
It is potassium peroxydisulfate, sodium peroxydisulfate, Ammonium persulfate. that described initiator is preferably initiator.
In step (): 0.5～1h is stirred with the mixing speed of 200～300 r/min.
In step (two): placing 10-20 minute after Deca monomer one, monomer two makes monomer one, monomer two to organosilicon kind
Son carries out swelling.
The organic-silicon-modified fluorine-contaninig polyacrylate waterproof and oilproof emulsion of the present invention utilizes organosilicon to fluorinated acrylate
Processed, compared with prior art be there is beneficial effect following outstanding:
(1) because the electronegativity of f is very big, the c-c main chain surrounding in fluoropolymer is by a series of electronegative f atoms
Surround, shielding protection is formed to main chain and interior molecules, make fluoropolymer latex film chemistry and its stablize, show excellent
Good weatherability and heat stability.Additionally, fluoro-containing group has the stronger phenotype that becomes, can effectively reduce the surface of polymeric film freely
Energy.Copolymerization is carried out using fluorochemical monomer and acrylic ester monomer, good film-forming property, the adhesive force of acrylic acid ester emulsion can be retained
High the advantages of, it is also equipped with the hydrophobic oleophobic performance of uniqueness, the contact angle on its film surface is larger.
(2) in the shape of a spiral, methyl outwards arranges and with main chain rotation silicone molecules structure, and molecule molal volume is big, interior
Cumulative density is low, and surface tension is little, imparts organic siliconresin excellent hydrophobic, water resistance.
(3) preparation process is simple, is more beneficial for large-scale industrialization promotion application.
Specific embodiment
Reference description organic-silicon-modified fluorine-contaninig polyacrylate waterproof and oilproof emulsion to the present invention with specific embodiment
And preparation method thereof be described in detail below.
Embodiment:
Embodiment one
Preparation process:
(1) add organosilicon list in the four-hole boiling flask equipped with agitator, Dropping funnel, thermometer and reflux condenser
Body octamethylcy-clotetrasiloxane 6g, emulsifier sodium lauryl sulfate and octyl phenol polyoxyethylene ether are in the ratio of 1:1.2
Add 0.6g, water 65g and catalyst sodium peroxydisulfate 0.2g, stir 0.5h under 205 r/min.
(2) after being allowed to abundant pre-emulsification, it is warmed up to 80 DEG C, make organic silicon monomer carry out ring-opening polymerization, maintain 2h,
Then cool to 50 DEG C, butyl acrylate and methyl methacrylate add 30g(monomer one in the ratio of 1:1.2), Deca first
Base hexafluorobutyl acrylate 3.9g(monomer two), it is swelling that placement a period of time makes monomer one, monomer two that organic silicon seed is carried out.
(3) and then be warmed up to 75 DEG C, it is initially charged sodium thiosulfate 0.5g, adds initiator ammonium persulfate 0.3g, emulsion
Moment has milky to be changed into translucent light blue, after to be triggered dose adds, reacts 2h, makes monomer one, monomer two and organosilicon
Monomer reaction fully, that is, obtains organic-silicon-modified fluorine-contaninig polyacrylate waterproof and oilproof emulsion.
Embodiment two
Preparation process:
(1) add organosilicon list in the four-hole boiling flask equipped with agitator, Dropping funnel, thermometer and reflux condenser
Body octamethylcy-clotetrasiloxane 6.9g, emulsifier sodium lauryl sulfate 0.6g, water 65g and catalyst potassium peroxydisulfate 0.2g,
1h is stirred under 250r/min.
(2) after being allowed to abundant pre-emulsification, it is warmed up to 85 DEG C, make organic silicon monomer carry out ring-opening polymerization, maintain 3h,
Then 50 DEG C are cooled to, butyl acrylate and methyl methacrylate add 30g, (monomer one) Deca methyl in the ratio of 1:1
Hexafluorobutyl acrylate 3.9g(monomer two), it is swelling that placement a period of time makes monomer one, monomer two that organic silicon seed is carried out.
(3) and then be warmed up to 75 DEG C, it is initially charged sodium thiosulfate 0.5g, adds initiator ammonium persulfate 0.3g, emulsion
Moment has milky to be changed into translucent light blue, after to be triggered dose adds, reacts 2h, makes monomer one, monomer two and organosilicon
Monomer reaction fully, that is, obtains organic-silicon-modified fluorine-contaninig polyacrylate waterproof and oilproof emulsion.
Embodiment three
Preparation process:
(1) add organosilicon list in the four-hole boiling flask equipped with agitator, Dropping funnel, thermometer and reflux condenser
Body octamethylcy-clotetrasiloxane 3.8g, vinyl triethoxyl siloxanes 4g, emulsifying agent octyl phenol polyoxyethylene ether -10
0.6g, water 65g and catalyst sodium peroxydisulfate 0.2g, stir 1h under 280r/min.
(2) after being allowed to abundant pre-emulsification, it is warmed up to 83 DEG C, makes organic silicon monomer carry out ring-opening polymerization, maintain
2.5h, then cools to 50 DEG C, and butyl acrylate and methyl methacrylate add 30g(monomer one in the ratio of 1:1.5), drip
Methylate hexafluorobutyl acrylate 3.9g(monomer two), place and make monomer one, monomer two that organic silicon seed is carried out for a period of time
Swelling.
(3) and then be warmed up to 75 DEG C, it is initially charged sodium thiosulfate 0.5g, adds initiator ammonium persulfate 0.3g, emulsion
Moment has milky to be changed into translucent light blue, after to be triggered dose adds, reacts 2h, makes monomer one, monomer two and organosilicon
Monomer reaction fully, that is, obtains organic-silicon-modified fluorine-contaninig polyacrylate waterproof and oilproof emulsion.
Test example one
The detection of hydrophobic performance
Emulsion obtained by experiment is applied directly on the sheet glass of cleaning, heat treatment temperature is 120 DEG C, is annealed into
Film.The mensure of water absorption rate: take a fritter film, claim its quality m1, it is placed in water immersion 48h, taking-up filter paper blots surface water
Point, claim its quality m2, the percent that after calculating immersion, film quality increases.The mensure of co-polymer membrane contact angle: take 8cm ×
The strip film of 2cm, with water for measuring liquid (liquid-drop diameter is for 1～2mm), with sessile drop method on jy-82 type contact angle instrument
Measure the contact angle to water for the latex film positive and negative.Measure in 1min and finish, each batten takes 6 points, (is spaced not between measuring point
Less than 1cm), remove arithmetic average.
Measured result such as table 1, wherein comparison 1 are the not fluorine-containing, acrylic emulsion without organosilicon, and comparison 2 is fluorine-containing third
Olefin(e) acid emulsion.
Table 1 emulsion water-proof
| Sample | Comparison 1 | Comparison 2 | Embodiment one | Embodiment two | Embodiment three |
| Film property | Well | Well | Well | Well | Well |
| Water absorption rate/(%) | 18.6 | 13.4 | 8.9 | 7.5 | 6.4 |
| Contact angle/(°) | 76.8 | 88.4 | 91.8 | 92.7 | 93.8 |
As it can be seen from table 1 the water absorption rate of gained emulsion of the present invention is substantially than traditional acrylic emulsion and fluorine-containing propene
Yogurt liquid low.
Test example two
The test of oil preventing performance
According to People's Republic of China's professional standard one coated fabric oil repellent assay method: using different surfaces tension force
The series of standards test fluid that Hydrocarbon is formed, drops in coated fabric surface, observes Wet Out.Grease proofing grade is to knit
The highest ranking of the non-wetted test liquid in thing surface determines.Grease proofing classification standard is shown in Table 2.Sample treatment: will obtain
Lotion applicator on bafta, toast certain time under uniform temperature, the sample that fabric is cut into 3 × 3cm specification can obtain
To fabric sample to be measured.Take the sample of 3 × 3cm specification, sample needs smooth, no folding line.Inhale 1 grade of standard of a pipe with syringe
Test solution, keeps at a certain distance away in fabric face and drips 2 droplets simultaneously, every diameter about 5mm, observes drop at 10 seconds with 45° angle
The Wet Out of clock.If sample is nonwetting, in the higher leveled standard solution of Deca, observe 10 seconds, continue this operation, directly
To having obvious moistening after certain grade of standard solution drops in sample upper 10 second.Make specimen surface last grade non-wetted
For grease proofing grade.
The grease proofing rank of table 2
Table 3 emulsion grease proofness
| Sample controls 1 compare 2 embodiment, one embodiment two embodiment three |
| Grease proofing grade 246 6～7 7 |
There is table 3 as can be seen that the grease proofness of gained emulsion of the present invention is substantially than traditional acrylic emulsion and fluorine-containing propene
The height of yogurt liquid.
Claims (6)
1. a kind of organic-silicon-modified fluorine-contaninig polyacrylate waterproof and oilproof emulsion it is characterised in that: this emulsion is joined by following weight
The raw material of ratio is obtained:
Organic silicon monomer 5-8 part；
Emulsifying agent 0.5-0.7 part；
Catalyst 0.1-0.3 part；
Monomer one 20-40 part；
Monomer two 3-5 part；
Sodium thiosulfate 0.4-0.6 part；
Initiator 0.2-0.4 part；
65 parts of water；
Described catalyst is potassium peroxydisulfate or sodium peroxydisulfate；
Described monomer one is mixture, methyl methacrylate and the butyl acrylate of methyl methacrylate and butyl acrylate
Mass ratio be 1/1.5～1.5/1；
Described monomer two is Hexafluorobutyl mathacrylate；
Preparation method comprises the following steps:
(1) organic silicon monomer, emulsifying agent, water and the catalyst of metering are added in reaction vessel, high-speed stirred is to fully pre- breast
Change；
(2) after pre-emulsification, it is warmed up to 80～85 DEG C, make organic silicon monomer carry out ring-opening polymerization, maintain 2～3h, then drop
Temperature arrives 40-60 DEG C, Deca monomer one, monomer two, and it is molten that placement a period of time makes monomer one, monomer two that organic silicon seed is carried out
Swollen；
(3) it is warmed up to 70～80 DEG C, is initially charged sodium thiosulfate, add initiator, emulsion moment is changed into semi-transparent from milky
Bright is light blue, after to be triggered dose adds, reacts 1-4h, makes monomer one, monomer two and organic silicon monomer reaction completely, that is, obtains
Organic-silicon-modified fluorinated acrylate waterproof and oilproof emulsion.
2. organic-silicon-modified fluorine-contaninig polyacrylate waterproof and oilproof emulsion according to claim 1 is it is characterised in that described
Organic silicon monomer is octamethylcy-clotetrasiloxane.
3. organic-silicon-modified fluorine-contaninig polyacrylate waterproof and oilproof emulsion according to claim 1 is it is characterised in that described
Emulsifying agent is sodium lauryl sulphate and/or octyl phenol polyoxyethylene ether -10.
4. organic-silicon-modified fluorine-contaninig polyacrylate waterproof and oilproof emulsion according to claim 1 is it is characterised in that described
Initiator is potassium peroxydisulfate, sodium peroxydisulfate, Ammonium persulfate..
5. organic-silicon-modified fluorine-contaninig polyacrylate waterproof and oilproof emulsion according to claim 1 is it is characterised in that step
(1) in: 0.5～1h is stirred with the mixing speed of 200～300 r/min.
6. organic-silicon-modified fluorine-contaninig polyacrylate waterproof and oilproof emulsion according to claim 1 is it is characterised in that step
(2) in: placing 10-30 minute after Deca monomer one, monomer two, to make monomer one, monomer two that organic silicon seed is carried out swelling.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106120442B (en) * | 2016-06-30 | 2017-10-24 | 上海锐瀚新材料科技有限公司 | A kind of anti-sticking emulsion of waterborne organic silicon and preparation method thereof |
| CN107814586B (en) * | 2017-10-26 | 2020-11-06 | 杭州瑞江新材料技术有限公司 | Organic silicon waterproof and oilproof emulsion and preparation method thereof |
| CN109591406B (en) * | 2018-12-27 | 2020-12-11 | 浙江东进新材料有限公司 | Waterproof moisture permeable composite fabric |
| CN109610218B (en) * | 2019-01-04 | 2021-04-06 | 浙江恒达新材料股份有限公司 | Preparation method and application of oil-proof plant microfibril or oil-proof nanocellulose |
| CN112195682B (en) * | 2020-10-09 | 2022-10-21 | 京准化工技术(上海)有限公司 | Waterproof and oilproof environment-friendly fluorine-free coating and preparation method thereof |
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|---|---|---|---|---|
| CN101016697A (en) * | 2007-02-15 | 2007-08-15 | 浙江工业大学 | Method of preparing fluorine and silicon containing hydrophobic and oil repellent fabric finishing agent |
| CN101302277A (en) * | 2008-06-16 | 2008-11-12 | 宁波润禾化学工业有限公司 | Functional fabric waterproof stiffener and preparation technology thereof |
| CN103396687A (en) * | 2013-06-27 | 2013-11-20 | 中科院广州化学有限公司 | Paint containing siloxane organic fluorine modified (methyl) acrylate polymer emulsion |
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2014
- 2014-03-20 CN CN201410103731.9A patent/CN103910833B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101016697A (en) * | 2007-02-15 | 2007-08-15 | 浙江工业大学 | Method of preparing fluorine and silicon containing hydrophobic and oil repellent fabric finishing agent |
| CN101302277A (en) * | 2008-06-16 | 2008-11-12 | 宁波润禾化学工业有限公司 | Functional fabric waterproof stiffener and preparation technology thereof |
| CN103396687A (en) * | 2013-06-27 | 2013-11-20 | 中科院广州化学有限公司 | Paint containing siloxane organic fluorine modified (methyl) acrylate polymer emulsion |
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