CN106188402B - A kind of waterborne epoxy modified acrylic lotion and preparation method thereof - Google Patents
A kind of waterborne epoxy modified acrylic lotion and preparation method thereof Download PDFInfo
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- CN106188402B CN106188402B CN201610531711.0A CN201610531711A CN106188402B CN 106188402 B CN106188402 B CN 106188402B CN 201610531711 A CN201610531711 A CN 201610531711A CN 106188402 B CN106188402 B CN 106188402B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/16—Sizing or water-repelling agents
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- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a kind of waterborne epoxy modified acrylic lotions and preparation method thereof, this method uses the monomer pre-emulsion containing epoxychloropropane first, under the compound action that emulsifier, starch form, nanoemulsions polymerization is carried out, waterborne epoxy modified acrylic lotion has been obtained.The glass transition temperature of the product emulsion is between 25 5 DEG C, and content is 25 50%, and particle size range is in 60 300nm.The product of the present invention has the characteristics that cohesive force is strong, is easy to form a film, resisting high-temperature yellowing function admirable, can assign paper or excellent water-resistance, tensile strength and the resisting high-temperature yellowing performance of fabric.
Description
Technical field
The present invention relates to a kind of waterborne epoxy modified acrylic lotions and preparation method thereof.
Background technology
In recent years, the attention with people to environmental protection, environmentally friendly product increasingly receive universal concern.Water
Property acrylic emulsion, because have many advantages, such as nontoxic, non-environmental-pollution, it is nonflammable explosive, easy to use due to be increasingly becoming and work as
The mainstream kind of preceding coating and adhesive.
Wallpaper is also at wallpaper, as a kind of indoor hardware fitting, be widely used in house, office, hotel interior
Finishing etc..Because with color is various, pattern is abundant, luxurious style, safety and environmental protection, easy for construction, affordable etc. it is a variety of its
The incomparable feature of its house decorative material, is increasingly liked by people.But most of wallpaper water proofing properties are poor, meet
The weather paper such as humidity, wet weather is easy to soften, wrinkle, and cohesive force declines to a great extent, influences to use.
Invention content
The purpose of the present invention is providing a kind of waterborne epoxy modified acrylic lotion and preparation method thereof, what this method obtained
Product and paper fiber binding force is strong, water-resistance is good, can avoid the facing papers such as wallpaper, wallpaper get damp and yellowing phenomenon.
The purpose of the present invention is what is be achieved through the following technical solutions：A kind of waterborne epoxy modified acrylic lotion, glass
Glass temperature is between -25-5 DEG C, and particle size range is in 60-300nm, solid content 25-50%.
A kind of preparation method of waterborne epoxy modified acrylic lotion, includes the following steps：
(1) by the water of 200 parts by weight, the unsaturated olefin and 5-50 of the emulsifier of 6-16 parts by weight, 600-900 parts by weight
The epoxychloropropane of parts by weight after mixing, stirs 0.5~10h, obtains monomer pre-emulsion.By the initiator of 0.2-11 parts by weight
It is uniformly mixed with the water of 100 parts by weight, obtains initiator solution.
(2) by the water of 1500 parts by weight, the starch of 100-300 parts by weight, the emulsifier of 1-6 parts by weight, 0.2 parts by weight
Amylase after mixing, leads to nitrogen 30min, is warming up to 80-95 DEG C.Sequentially add partial monosomy pre-emulsion (total amount
10%), part initiator aqueous solution (30wt% of initiator solution total amount).After mixing, while remaining list is added dropwise
Body pre-emulsion, initiator solution, time for adding 1-5h.Keep the temperature 0.5-3h.Cooling, with 150 mesh screens, obtains aqueous ring
Oxygen modified acrylic acid emulsion.
Further, the unsaturated olefin by styrene, α-methylstyrene, contain C1-C4The styrene of substituent group, third
E pioic acid methyl ester, ethyl acrylate, propyl acrylate, butyl acrylate, tert-butyl acrylate, Isooctyl acrylate monomer, acrylamide,
Hydroxymethyl acrylamide, Methacrylamide, acrylic acid, methacrylic acid, dimethylaminoethyl methacrylate, acrylic acid two
Methylamino ethyl ester, diallylamine, diallyl ammonium chloride any one or more of are formed according to arbitrary proportioning.
Further, the emulsifier is by fatty alcohol polyoxyethylene ether AEO, alkyl phenol polyoxyethylene ether (including nonyl
Phenol polyethenoxy ether NP, octyl phenol polyoxyethylene ether OP and TX), alkyl diphenyl base ether sodium disulfonate (DB-45), polyoxyethylene nonyl phenyl
Vinethene ammonium sulfate (CO-436), lauryl sodium sulfate (K12), dodecyl sodium sulfate (SDS), dodecyl benzene sulfonic acid
Any one or more of sodium (SDBS) form according to arbitrary proportioning.
Further, the initiator is ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate, persulphate-bisulphite
Any one of sodium, azo-bis-isobutyrate hydrochloride or azo diisopropylamidinateand oxazoline hydrochloride.
Further, the starch is：Cassava ative starch, cassava modified starch or cassava oxidized starch.
7. according to the method described in claim 2, it is characterized in that, in the step 1, unsaturated olefin is acrylic acid uncle
The mass ratio of butyl ester, unsaturated olefin and epoxychloropropane is 15~35:1.
Further, the waterborne epoxy modified acrylic lotion is a kind of particle size range in 60-300nm, solid content
Content is 25-50%, macromolecule emulsion of the glass transition temperature between -25-5 DEG C.
The beneficial effects of the present invention are：The present invention is bonded by unique nanoemulsions preparation process, product and fabric
Power is strong, is easy to that film forming, high temperature anti-yellowing property are excellent, can assign paper or excellent water-resistance, tensile strength and the Nai Gao of fabric
Warm xanthochromia performance.
Specific implementation mode
Embodiment 1：A kind of preparation method of waterborne epoxy modified acrylic lotion, includes the following steps：
(1) by the lauryl sodium sulfate (K12) of fatty alcohol polyoxyethylene ether AEO-9,7g of the water of 200g, 6g, 210g
Styrene, the butyl acrylate of 525g, 60g methyl methacrylates, 5g acrylic acid and weight as shown in table 1 epoxy chloropropionate
Alkane after mixing, stirs 1h, obtains monomer pre-emulsion.The water of 2g potassium peroxydisulfates and 100g is uniformly mixed, it is water-soluble to obtain initiator
Liquid.
(2) by 1500g water, 150g cassavas ative starch, 1g K12,0.2g amylase after mixing, lead to nitrogen 30min,
It is warming up to 85 DEG C.Sequentially add partial monosomy pre-emulsion (10wt% of total amount), part initiator aqueous solution (initiator solution
The 30wt% of total amount).After mixing, while remaining monomer pre-emulsion, initiator solution, time for adding 3h is added dropwise.
Keep the temperature 1h.Cooling, with 150 mesh screens, obtains 1~A9 of waterborne epoxy modified acrylic latex A.
Waterborne epoxy modified acrylic 1~A9 of latex A that 200g is prepared, being diluted to solid content with tap water is
25%, by body paper (80g/m2Qualitative filter paper) it is put into immersion 30 seconds, taking-up is directly placed into air dry oven and dries 10 minutes, and room temperature is put
It sets 2 hours.
Hygroscopicity value measures：Using Hangzhou Zhi Bang Autotek S. r. l. ZB-COBB125 types can vigorous water absorption meter, press
GB/T1540-1989 methods detect pattern to be measured.
Other measurement：Tensile strength is drawn using the ZB-WL300 type horizontal computers of Hangzhou Zhi Bang Autotek S. r. l.
Power instrument；Burst index uses the ZB-NPY1600 type paper burst testers of Hangzhou Zhi Bang Autotek S. r. l.；It is resistance to
Folding degree uses the ZB-NZ135 type folding testers of Hangzhou Zhi Bang Autotek S. r. l..
The physical characteristic of 1 example of table, one product
The performance test of 2 example of table, one product
Note：Data above is the mean value obtained by 10 parallel tests.
It can be seen that from upper Tables 1 and 2 when the amount of epoxychloropropane is 35g, the grain size of product reaches 137nm, production
Object shows higher mechanical property and water resistance.Show epoxychloropropane in starch conversion by multiple comparison test
In emulsion system, the epoxy group with reactivity can be formed.These epoxy groups, can further with the hydroxyl in paper fiber
Strong Covalent bonding together effect occurs for the groups such as base, carboxyl, to the water-resistance of paper, tensile strength and the anti-energy that gets damp
Power is obviously improved effect.When the amount of epoxychloropropane is more than 55g, due to the epoxy group density of lotion microsphere surface
Greatly, hardness is higher after product film forming, can influence the pliability and feel of paper；Meanwhile the chemical stability for easily causing product becomes
Difference, shortened shelf life.When the amount of epoxychloropropane is less than 25g, since the ratio of epoxy group is too small, product and fiber molecule
Between chemical bonding active force it is weaker, water-resistance and anti-performance of getting damp are poor.According to test result analysis, when unsaturated olefin list
The mass ratio of body and epoxychloropropane is 14.55~32:When 1, the application effect of product is best.
Embodiment 2：A kind of preparation method of waterborne epoxy modified acrylic lotion, includes the following steps：
(1) by the neopelex (SDBS) of octyl phenol polyoxyethylene ether OP-10,9g of the water of 200g, 7g,
The α-methylstyrene of 80g, the butyl acrylate of 450g, 32g Isooctyl acrylate monomers, 10g methyl methacrylates, 5g acrylic acid
After mixing with the epoxychloropropane of 35g, 1h is stirred, monomer pre-emulsion is obtained.By 0.2 azo-bis-isobutyrate hydrochloride and 100g
Water be uniformly mixed, obtain initiator solution.
(2) by 1500g water, 100g cassavas ative starch, 3g SDBS, 0.2g amylase after mixing, lead to nitrogen
30min is warming up to 95 DEG C.Monomer pre-emulsion and initiator solution is added dropwise in the way of B1~B5 respectively.Time for adding is
1h.Keep the temperature 3h.Cooling, with 150 mesh screens, obtains waterborne epoxy modified acrylic lotion.
B1：It is disposable to be added dropwise；
B2：Monomer pre-emulsion, the 5wt% initiator solutions of 5wt% are first sequentially added, stirs 20min, then 95wt%
Monomer pre-emulsion and 95wt% initiator solution.
B3：The first monomer pre-emulsion of 10wt%, 10wt% initiator solutions successively stir 20min, then 90wt%
The initiator solution of monomer pre-emulsion and 90wt%.
B4：The first monomer pre-emulsion of 15wt%, 15wt% initiator solutions successively stir 20min, then 85wt%
The initiator solution of monomer pre-emulsion and 85wt%.
B5：The first monomer pre-emulsion of 20wt%, 20wt% initiator solutions successively stir 20min, then 80wt%
The initiator solution of monomer pre-emulsion and 80wt%.
The Cypres that the present embodiment obtains are measured according to method described in embodiment 1, measurement result such as table 3
It is shown.
The physical characteristic and application performance test of 3 example of table, two product
Note：Data above is the mean value obtained by 10 parallel tests.
From upper table it can also be seen that monomer pre-emulsion and the dropwise addition process of initiator solution have weight for properties of product
It influences, the dropwise addition of the two should quantify dropwise addition-size tunable principle, and the dropwise addition mode and process of monomer pre-emulsion determine kind
The grain size and quality of sub- lotion, and then influence the particle size and distribution situation of final Cypres product.Test of many times is demonstrate,proved
It is bright, when the additive amount for the first time of monomer pre-emulsion, initiator accounts for the 10% of total amount, it then follows the reaction of quantitative dropwise addition-size tunable
Mechanism, between the grain size 120-150nm of product and narrow distribution range, product paper permeability and sizing efficiency most
It is good, thus there is excellent water-resistance, moisture resistance and tensile strength.Process, the formation of product seed is added dropwise using disposable
Process is random, and the uniform particle diameter for be easy to causeing final products is poor, particle diameter distribution is too wide, influences the water resistant of product Process of Applying Glue
Performance.When the amount being added dropwise for the first time is less than 10%, seed amount is less, and the grain size of product is bigger than normal, and product is opaque poor, product
Ratio in paper is penetrated into Process of Applying Glue and density is smaller, thus sizing efficiency is poor.When the amount being added dropwise for the first time is higher than
When 10%, the grain size of product is less than normal, and the viscosity for be easy to causeing the reaction later stage is bigger than normal, and mechanical agitation is difficult, product be easy implode and
Demulsification.
Embodiment 3：A kind of preparation method of waterborne epoxy modified acrylic lotion, includes the following steps：
(1) by the water of 200 parts by weight, the nonylphenol polyoxyethylene ether NP-10 of 3 parts by weight, the CO-436 of 6 parts by weight, 600
Parts by weight unsaturated olefin (composition is as shown in table 4) and the epoxychloropropane of 35 parts by weight after mixing, stir 0.5h, obtain list
Body pre-emulsion.The water of the azo diisopropylamidinateand oxazoline hydrochloride of 0.2 parts by weight and 100 parts by weight is uniformly mixed, must be caused
Agent aqueous solution.
(2) by the water of 1500 parts by weight, the cassava oxidized starch of 100 parts by weight, the CO-436 of 1 parts by weight, 0.2 parts by weight
Amylase after mixing, lead to nitrogen 30min, be warming up to 95 DEG C.Sequentially add partial monosomy pre-emulsion (total amount
10wt%), part initiator aqueous solution (30wt% of initiator solution total amount).After mixing, it while being added dropwise remaining
Monomer pre-emulsion, initiator solution, time for adding 5h.Keep the temperature 1h.Cooling, with 150 mesh screens, obtains water-base epoxy and changes
Property acrylic emulsion.
The Cypres that the present embodiment obtains are measured according to method described in embodiment 1, measurement result such as table 4
Shown in 5.
The material of 4 example of table, three product is matched and physical characteristic
| Product | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 |
| Styrene | 70% | 60% | 50% | 40% | 35% | 30% | 25% | 10% |
| Butyl acrylate | 27.5% | 37.5% | 47.5% | 57.5% | 62.5% | 67.5% | 72.5% | 87.5% |
| Hydroxymethyl acrylamide | 1.5% | 1.5% | 1.5% | 1.5% | 1.5% | 1.5% | 1.5% | 1.5% |
| Acrylic acid | 1% | 1% | 1% | 1% | 1% | 1% | 1% | 1% |
| Solid content (wt%) | 34 | 43 | 44 | 43 | 29 | 33 | 42 | 48 |
| Grain size (nm) | 152 | 143 | 133 | 145 | 134 | 144 | 143 | 152 |
| Glass transition temperature (DEG C) | 39.8 | 22.1 | 5.0 | -7.1 | -13.6 | -18.5 | -25.0 | -40.1 |
The performance test of 5 example of table, three product
Note：Data above is the mean value obtained by 10 parallel tests.
Analysis：The proportioning of unsaturated olefin determines the glass transition temperature of product, and then influences the application effect of product.Instead
Retrial verification is bright, and between -25~5 DEG C, product can assign the excellent flexibility of paper, feel and resist the glass transition temperature of product
Aqueous energy is equal.When the glass transition temperature of product is less than -25 DEG C, feel is partially soft under room temperature for product, although burst index, resistance to
Folding degree is preferable, but water-resistance is poor, and the phenomenon that be easy to cause paper machine roll banding using process.When the glass transition temperature of product is higher than
At 5 DEG C, feel is partially hard under room temperature, toughness is poor for product, thus loses the meaning of application.
Claims (4)
1. a kind of preparation method of waterborne epoxy modified acrylic lotion, which is characterized in that include the following steps：
（1）By the water of 200 parts by weight, the emulsifier of 6-16 parts by weight, the unsaturated olefin of 600-900 parts by weight and 5-50 weight
The epoxychloropropane of part after mixing, stirs 0.5 ~ 10h, obtains monomer pre-emulsion；By the initiator of 0.2-11 parts by weight and 100
The water of parts by weight is uniformly mixed, and obtains initiator solution；
Wherein, unsaturated olefin is by methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, the tertiary fourth of acrylic acid
Ester, Isooctyl acrylate monomer, acrylamide, hydroxymethyl acrylamide, Methacrylamide, acrylic acid, methacrylic acid, methyl-prop
Olefin(e) acid dimethylaminoethyl, dimethylaminoethyl acrylate any one or more of are formed according to arbitrary proportioning；And it is described not
The mass ratio of saturation of olefins and epoxychloropropane is 14.55 ~ 32:1；
（2）By the water of 1500 parts by weight, the starch of the starch of 100-300 parts by weight, the emulsifier of 1-6 parts by weight, 0.2 parts by weight
Enzyme after mixing, leads to nitrogen 30min, is warming up to 80-95 DEG C；It is water-soluble to sequentially add partial monosomy pre-emulsion, part initiator
Liquid, wherein partial monosomy pre-emulsion accounts for the 10wt% of monomer pre-emulsion total amount, and part initiator aqueous solution accounts for initiator solution
The 30wt% of total amount；After mixing, while remaining monomer pre-emulsion, initiator solution, time for adding 1-5h is added dropwise；
Keep the temperature 0.5-3h；Cooling, with 150 mesh screens, obtains waterborne epoxy modified acrylic lotion.
2. preparation method according to claim 1, which is characterized in that the emulsifier is by fatty alcohol polyoxyethylene ether
AEO, alkyl phenol polyoxyethylene ether, alkyl diphenyl base ether sodium disulfonate, nonylphenol polyoxyethylene ether ammonium sulfate, dodecyl sulphur
Sour sodium, dodecyl sodium sulfate, any one or more of neopelex form according to arbitrary proportioning.
3. preparation method according to claim 1, which is characterized in that the initiator be ammonium persulfate, sodium peroxydisulfate,
In potassium peroxydisulfate, persulphate-bisulphite sodium, azo-bis-isobutyrate hydrochloride or azo diisopropylamidinateand oxazoline hydrochloride
It is any.
4. preparation method according to claim 1, which is characterized in that the starch is：Cassava ative starch, cassava denaturation are formed sediment
Powder or cassava oxidized starch.
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| CN114990930A (en) * | 2022-05-28 | 2022-09-02 | 吉翔宝（太仓）离型材料科技发展有限公司 | High-temperature-resistance and solvent-resistance PU leather release paper and preparation process thereof |
| CN116284949A (en) * | 2023-05-22 | 2023-06-23 | 广讯检测（广东）有限公司 | Preparation method of epoxy-acrylic resin modified superfine azo-dicarboxamide and emulsion thereof |
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| CN100338305C (en) * | 2004-03-11 | 2007-09-19 | 大连广汇化学有限公司 | Method for preparing amphiprotic intensifier for paper |
| CN101429742B (en) * | 2008-12-08 | 2010-10-06 | 浙江传化华洋化工有限公司 | Surface sizing additive for papermaking |
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