CN104151481B - Acrylic ester copolymer emulsion and preparation method thereof - Google Patents
Acrylic ester copolymer emulsion and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an acrylic ester copolymer emulsion and a preparation method thereof. The acrylic ester copolymer emulsion is prepared from the following raw materials in percentage by weight: 10%-25% of alkyl methacrylate, 10%-30% of alkyl acrylate, 1%-5% of hydroxyalkanoate, 1%-5% of alkyl carboxylic acid, 0.5%-5% of acrylamide, 0.1%-1% of hydrazide, 0.25%-0.5% of initiating agents and 0.5%-1.5% of emulsifying agents. Compared with the traditional acrylic ester copolymer, the acrylic ester copolymer emulsion disclosed by the invention has the advantages that the glass temperature of a polymer which forms a colloidal particle is gradually changed from the center to surface of the colloidal particle and an internally-plasticized cross-linking functional monomer is introduced; the prepared emulsion has very good film-forming property; the formed film is high in rigidity, can be used for preparing redispersible polymer latex powder and meets the requirements of various high-property coatings.
Description
Technical field
The present invention relates to a kind of acrylate polymer emulsion, more particularly to a kind of acrylate polymer emulsion and its
Preparation method.
Background technology
Redispersible Polymeric Emulsion Powder is that polymer emulsion drying powdering techniques obtain a kind of free flowable powder
End, after the redispersion that adds water, can generate and the original regeneration emulsion that polymer emulsion performance is identical, purposes is similar.Prepare this
Polymer matrix emulsion and its latex powder, and the Dry Powder Architectural Paint developed on this basis has important economic implications and society
Meaning.Acrylic polymer with its excellent weatherability, resistance to water, resistance to acids and bases, stain resistant, nontoxic, to environment friend
The performance such as good, cheap is widely used in building material field.Preparation and exploitation acrylic polymer latexes become construction material
One new direction of research.But in existing acrylate conventional emulsion polymerization, emulsifying agent is low-molecular-weight parents' material, emulsifying
Agent be physical absorption on emulsion particle surface, in LS dry run, system is changed into single-phase from multiphase, low-molecular-weight breast
Agent is also easy to produce migration in preparation technology, departs from emulsion particle surface, causes the active substance on emulsion particle surface to lack, make latex
There is no when powder disperses in water redispersion performance.In addition, in order to meet film formation performance, the conventional breast of existing acrylate
The glass transition temperature ratio of liquid is relatively low, can stick together and lose redispersibility in spray drying.Patent is had to pass through to design
The emulsion being prepared for hard outside soft inside sticks together in spray-drying process to prepare Redispersible Polymeric Emulsion Powder to reduce, with
When in order to meet the redispersibility of latex powder, added a large amount of hydrophilic monomers, the Redispersible Polymeric Emulsion Powder of preparation in shell
Although having good mobility and redispersibility, the film poor water resistance that redispersion liquid becomes, and not film forming at low temperature, limit
The use of propylene esters redispersable latex powder.
Content of the invention
The purpose of the present invention is directed to the deficiency of the emulsion presence that above-mentioned redispersable latex powder uses, and provides a kind of group plastic
The polymer glass temperature (tg) of grain gradually changes from micelle center to surface, is simultaneously introduced and has internally plasticized cross-linking type work(
The acrylate polymer emulsion of energy monomer；This acrylate polymer emulsion has good film property, and institute's film forming is fine and close hard
Degree is high, can be used for the requirement prepared Redispersible Polymeric Emulsion Powder and meet various high-performance coatings.
For reaching above-mentioned purpose, the present invention is achieved in that
A kind of acrylate polymer emulsion, is made up of the component of following mass percent:
Wherein, acrylic amide is introduced into can not only improve on polymer chain acrylate polymer emulsion resistance to from
Sub- stability, can improve the adhesion strength of emulsion and base material simultaneously；And hydrazides can be reacted with alkyl carboxylic acid, reaction equation is such as
Under:
On the one hand the degree of cross linking and the resistance to water of polymer can be improved, improve the pliability of polymer molecular chain, fall simultaneously
The minimum film formation temperature of low emulsion is so that emulsion at low temperature being capable of film forming.
Described alkyl methacrylate is methyl methacrylate, ethyl methacrylate, propyl methacrylate, first
Base butyl acrylate, pentylmethacrylate, N-Hexyl methacrylate and/or 2-Propenoic acid, 2-methyl-, isooctyl ester.
Described alkyl acrylate is acrylic acid methyl ester., ethyl acrylate, propyl acrylate, butyl acrylate, acrylic acid
Pentyl ester, Hexyl 2-propenoate and/or Isooctyl acrylate monomer.
Described hydroxy alkyl ester be acrylic acid 2 hydroxy methacrylate, acrylic acid 3 hydroxy propyl ester, acrylic acid 2 hydroxybutyl,
Acrylic acid 5 hydroxyl pentyl ester, the own ester of acrylic acid 6 hydroxyl, methacrylic acid 2 hydroxy methacrylate and/or methacrylic acid 3 hydroxyl
Base propyl ester.
Described alkyl carboxylic acid is methacrylic acid and/or acrylic acid.
Described acrylic amide is acrylamide, Methacrylamide, n, n' methylene-bisacrylamide, n methylol
Acrylamide and/or n N-isopropylacrylamide, it is introduced on polymer chain and can not only improve acrylate polymer breast
The resistance to ion stability of liquid, can improve the adhesion strength of emulsion and base material simultaneously.
Described hydrazides is unifor, n, n' diacetyl hydrazine, maleic hydrazide, adipic dihydrazide and/or decanedioic acid
Two hydrazides, hydrazides can be reacted with alkyl carboxylic acid, and reaction equation is as follows, on the one hand improves the degree of cross linking and the resistance to water of polymer,
Improve the pliability of polymer molecular chain, the minimum film formation temperature reducing emulsion is so that emulsion at low temperature being capable of film forming simultaneously.
Described initiator is the persulfuric acid salt initiators such as potassium peroxydisulfate, sodium peroxydisulfate and/or Ammonium persulfate..
Described emulsifying agent is anion emulsifier and nonionic emulsifier compounds and forms, and anion emulsifier is dodecyl
Diphenyl ether disodium sulfonate (dsb), dodecylbenzene sodium sulfonate (las) and/or sodium lauryl sulphate (sds)；Non-ionic emulsifier
Agent is polysorbas20 (tween 20), Tween 80 (tween 80), polyoxyethylene Zhong Xin 2, 2-Oxydiphenol 10 (op 10) and/or nonyl phenol
Polyoxyethylene ether (tx 10), wherein anion emulsifier are the mechanical stabilities in order to improve emulsion, and nonionic emulsifier is
The ratio of both the ion stabilities in order to improve emulsion is 1:1 4:1.
Described water is preferably deionized water.
In acrylate polymer emulsion form micelle polymer glass temperature (tg) from micelle center to surface by
Gradual change, be simultaneously introduced have internal plasticization and crosslinked function hydrazides.
The preparation method of described acrylate polymer emulsion, the step that it includes is as follows:
A, by percentage to the quality, first by 10%～50% alkyl methacrylate in composition of raw materials, 50%～
The acrylic amide of 90% alkyl acrylate, 0～30% hydroxy alkyl ester, 0～30% alkyl carboxylic acid and 0～30% mixes
Mix monomer is made in conjunction；Again by remaining for formula ratio alkyl methacrylate, alkyl acrylate, hydroxy alkyl ester, alkyl carboxylic
Acid and acrylic amide are mixed and made into mix monomer；Mix monomer is controlled to be 1.8～2.5 with the mass ratio of mix monomer:
1；The polymers obtained vitrification point of mix monomer is less than the polymers obtained vitrification point of mix monomer, this
Sample both can ensure that emulsion did not sticked together in spray-drying process, can guarantee that again emulsion under room temperature or even low temperature film forming and
The hardness of institute's film forming is high；
B, preparation seed emulsion: the water of water gross mass 60%～80% will be accounted for, account for total emulsifiers quality 40%～60%
Emulsifying agent is added in reactor with the initiator accounting for initiator quality 40%～50%, and dispersed with stirring 10～20 minutes treats temperature
Degree rises to 78～85 DEG C, by the mix monomer of 5%～15% mass in 15～30 minutes instillation reactors, after completion of dropping
Insulation 15～30 minutes, prepared seed emulsion；
C, in 1.5～2 hours, 75%～85% mix monomer is uniformly added drop-wise to the seed emulsion that step b obtains
In, react 15～30 minutes after completion of dropping；Then remaining mix monomer and 10～20% mix monomer ii are uniformly mixed
Become mix monomer iii, and in 50～75 minutes, mix monomer iii is uniformly added drop-wise in above-mentioned emulsion, anti-after completion of dropping
Answer 15～30 minutes, the polymers obtained glass transition temperature of mix monomer iii is poly- obtained by mix monomer here
The vitrification point of compound and the polymers obtained vitrification point of mix monomer, thus avoid mix monomer gained
To polymer and mix monomer polymers obtained generation microphase-separated；Followed by by remaining mix monomer ii 1.5～2
Uniformly it is added drop-wise in above-mentioned emulsion in hour；While Deca monomer, remaining water, emulsifying agent and initiator are continuously added drop-wise to b
In the seed emulsion that step obtains, react 0.5～1 hour after completion of dropping, then be warming up to 80～90 DEG C and be incubated 0.5～1 hour,
Then it is cooled to 40～50 DEG C, with the filter-cloth filtering discharging of 100 mesh, obtain final product acrylate polymer emulsion.
Described emulsifier is the 0.5%～1.5% of all monomer gross mass.
Described initiator amount is the 0.25%～0.5% of all monomer gross mass.
Polymer glass temperature tg of described mix monomer preparation is 40～20 DEG C, described mix monomer preparation
Polymer glass temperature be 40～75 DEG C.
Compared with prior art, the present invention have as follows project effect:
1) in the present invention, using multi-step emulsion polymerization method, composition micelle in prepared acrylate polymer emulsion
Polymer glass temperature (tg) and gradually change so that redispersible poly- with the preparation of this kind of emulsion from micelle center to surface
After compound latex redispersion, film forming will not be separated, and has good redispersion performance and filming performance；
2) in the present invention, it is simultaneously introduced internal plasticization monomer and cross-linking monomer, the emulsion obtaining becomes under room temperature and low temperature
Film properties are all fine, and institute's film forming is fine and close, water-tolerant, the physical and chemical performance of polymer, mechanical performance and adhesive property simultaneously
Improved.
3) emulsion of the present invention can be obtained redispersion liquid particle diameter under conditions of being spray-dried and be less than the redispersible of 150nm
Polymer emulsion powder, the Nano Particle of redispersion liquid also ensure that the good redispersibility of latex powder and the film forming of redispersion liquid
Performance, can meet the requirement to latex powder film property for the various high-performance coatings, be widely used in dry powder latex paint, dry powder gluing
Agent, inner-outer wall building putties, gravity flow self-leveling floor mortar, plastering material and insulation material etc..
Brief description
Fig. 1 is embodiment 1 Central Plains emulsion tem figure.
Fig. 2 is redispersion emulsion tem figure in embodiment 1.
Fig. 3 is that embodiment 1 Central Plains emulsion film forming sem schemes.
Fig. 4 is redispersion emulsion film forming sem figure in embodiment 1.
Specific embodiment
With reference to embodiment, the invention will be further described, it should be noted that embodiment is not constituted to this
The restriction of the claimed scope of invention.
Relevant test method illustrates:
1) particle diameter: diluted sample is contained about 3 ‰, ultrasonic 3min to solid, using the zs producing from malvern company of Britain
Nano s Malvern nanometer particle size tester records.
2) tem: sample deionized water is diluted to and coats on copper mesh after admittedly containing about 3 ‰, then contained for 3% with solid
Phosphotungstic acid dyes 2 minutes, is used for tem and tests after natural drying.Using transmission electron microscope tecnai 12 (Dutch fei electronics
Optical Co., Ltd) analysis can get emulsion system microscopic pattern, during operation accelerating potential be 80kv.
3) sem: latex film (25 DEG C drying 7 days) is put into makes its natural fracture in liquid nitrogen, latex film is bonded at conducting resinl
On, then metal spraying is processed, and observes the plane of disruption of latex film.Using Dutch nova nanosem 430 high power scanning electron microscopy
Mirror, its accelerating potential is 20kv, and the scan period is 100s, and pulsimeter digit rate is 2000cps, and operating distance is 34mm.
4) phasor of afm: sample is measured not in contact with latex film (the 25 DEG C drying 7 days) surface crossed at room temperature by afm
Obtain, pattern is tapping-mode, test instrunment is bruker iconafm, probe model nanosensors ppp nch (spring
Constant 10 130n/m, resonant frequency 204 497khz).Rap power (rsp=a/a0 (the freely frequency of setpoint frequency/tip vibration
Rate)) it is 0.5 0.9, correspond to hard and soft rapping respectively.Using analysis software be nanoscopeanalysis
software.
5) minimum film formation temperature: using mfft bar (rhopint co.ltd, british) measurement polymer emulsion
Low film formation temperature, by sample from temperature end injection gradient plate groove, is scraped to low-temperature end from high temperature with scraper and draws, unnecessary sample is used
Rag is wiped.Form continuous hyaline membrane, cracking and Chalk phenomenon demarcation line after drying, read hyaline membrane and cracking film demarcation line
Temperature, as sample minimum film formation temperature.
6) nmr: replace h with heavy water2O configures nmr sample, after ready sample places 1d, measures sample with tms for external standard1H and13Cnmr composes.Instrument is unity inova 300 type nuclear magnetic resonance analyser (varian company), and all mensure are all at 40 DEG C
Carry out.
7) resistance to water: be measured according to gb/t 1,733 1993 paint film resistance to water algoscopy.
8) water absorption rate: be measured according to hg/t 3,344 2012 paint film water absorption rate algoscopy.
Embodiment 1:
The composition of acrylate polymer emulsion includes methyl methacrylate, butyl acrylate, acrylic acid 2 hydroxyl second
Ester, methacrylic acid, n n-methylolacrylamide, sebacic dihydrazide, its Ju Ti Pei Fang component such as table 1 below:
Table 1
The manufacture method of acrylate polymer emulsion, its step is as follows:
A, by the methyl methacrylate of above-mentioned quality, butyl acrylate, acrylic acid 2 hydroxy methacrylate, methacrylic acid,
N n-methylolacrylamide is mixed and made into mix monomer and mix monomer respectively by formula.According to fox formula, wherein mix
21.8 DEG C of the tg=of monomer composition copolymer, mix monomer forms tg=57.2 DEG C of copolymer.
B, preparation seed emulsion: the water of water gross mass 70% will be accounted for, account for the composite emulsifier of total emulsifiers quality 50%
(sds and tween20) and account for the initiator potassium persulfate of initiator quality 45% and be added in reactor, 15 points of dispersed with stirring
Clock, treats that temperature rises to 80 DEG C, by the mix monomer of 10% mass in 25 minutes instillation reactors, is incubated 30 after completion of dropping
Minute, prepared seed emulsion；
C, in 1.6 hours, 80% mix monomer is uniformly added drop-wise in the seed emulsion that step b obtains, completion of dropping
React 25 minutes afterwards；Then remaining mix monomer and 10% mix monomer ii are uniformly mixed into mix monomer iii, and
In 60 minutes, mix monomer iii is uniformly added drop-wise in above-mentioned emulsion, reacts 25 minutes after completion of dropping；Followed by will be remaining
Mix monomer ii was uniformly added drop-wise in above-mentioned emulsion in 2 hours；By remaining water, emulsifying agent and initiation while Deca monomer
Agent is continuously added drop-wise in the seed emulsion that b step obtains, and reacts 1 hour after completion of dropping, then it is little to be warming up to 85 DEG C of insulations 0.6
When, then it is cooled to 45 DEG C, filtering and discharging, obtain final product acrylate polymer emulsion.
The mean diameter testing the propylene polymer emulsion obtaining is 106nm, propylene polymer emulsion powder redispersion
The particle diameter of liquid is 120nm；The former emulsion of tem analysis shows (Fig. 1) become of uniform size with the latex particle of redispersion emulsion (Fig. 2)
Spherical, but the particle diameter of redispersion liquid is larger, and (the former emulsion of example below is similar to Example 1 with redispersion emulsion, not one by one
There is provided)；Sem analysis shows redispersion sol film (Fig. 4) and former emulsion film (Fig. 3) all have good filming performance, and
No phenomenon of phase separation (the redispersion sol film of example below is similar to Example 1 with former emulsion film, does not provide one by one)；Former
The minimum film formation temperature of emulsion is 0 DEG C, and the minimum film formation temperature of redispersion liquid is 2 DEG C；Nuclear magnetic resonance, NMR (nmr) analysis shows are obtained
Propylene polymer emulsion composition from micelle center to surface be in gradually change.Under conditions of being spray-dried, prepared
Redispersible Polymeric Emulsion Powder has higher yield, reaches more than 98%, and the Redispersible Polymeric Emulsion Powder tool being obtained
There are good powder fluidity, redispersibility and film property.The propylene that the resistance to water of redispersion sol film is more common can divide again
The 24h resistance to water of scattered latex is greatly improved, and water absorption rate is only 1.5%.
Embodiment 2
The composition of acrylate polymer emulsion include methyl methacrylate, butyl acrylate, Isooctyl acrylate monomer, third
Olefin(e) acid 2 hydroxy methacrylate, acrylic acid, n n-methylolacrylamide, adipic dihydrazide, its concrete component formula such as table 2 below:
Table 2
The manufacture method of acrylate polymer emulsion, its step is as follows:
A, by the methyl methacrylate of above-mentioned mass parts, butyl acrylate, Isooctyl acrylate monomer, acrylic acid 2 hydroxyl
Ethyl ester, acrylic acid, n n-methylolacrylamide, adipic dihydrazide are not mixed and made into mix monomer and mix monomer.According to fox
Formula, wherein mix monomer form 28.4 DEG C of the tg=of copolymer, and mix monomer forms tg=67.6 DEG C of copolymer.
B, preparation seed emulsion: the water of water gross mass 75% will be accounted for, the emulsifying agent accounting for total emulsifiers quality 55% draws with accounting for
The initiator sending out agent quality 40% is added in reactor, and dispersed with stirring 10 minutes treats that temperature rises to 83 DEG C, by 13% mass
Mix monomer, in 20 minutes instillation reactors, is incubated 30 minutes after completion of dropping, prepared seed emulsion；
C, in 2 hours, 80% mix monomer is uniformly added drop-wise in the seed emulsion that step b obtains, after completion of dropping
Reaction 30 minutes；Then remaining mix monomer and 20% mix monomer ii are uniformly mixed into mix monomer iii, and 72
In minute, mix monomer iii is uniformly added drop-wise in above-mentioned emulsion, reacts 15 minutes after completion of dropping；Followed by will be remaining mixed
Close monomer ii to be uniformly added drop-wise in above-mentioned emulsion in 1.5 hours；Remaining water, emulsifying agent and initiator while Deca monomer
Continuously it is added drop-wise in the seed emulsion that b step obtains, reacts 1 hour after completion of dropping, then be warming up to 82 DEG C and be incubated 1 hour, so
After be cooled to 43 DEG C, filtering and discharging, obtain final product acrylate polymer emulsion.
The mean diameter testing the propylene polymer emulsion obtaining is 105nm, propylene polymer emulsion powder redispersion
The particle diameter of liquid is 124nm；The former emulsion of tem analysis shows becomes of uniform size spherical with the latex particle of redispersion liquid, but divides again
The particle diameter of dispersion liquid is larger；Sem and Atomic Mechanics microscope (afm) analysis shows redispersion sol film are all had with former emulsion film
Good filming performance, and no phenomenon of phase separation；The minimum film formation temperature of former emulsion is 1 DEG C, the minimum film forming of redispersion liquid
Temperature is 2 DEG C；The composition of propylene polymer emulsion that nuclear magnetic resonance, NMR (nmr) analysis shows are obtained from micelle center to surface is in
Gradually change.
Under conditions of being spray-dried, prepared Redispersible Polymeric Emulsion Powder has higher yield, reaches more than 98%,
And the Redispersible Polymeric Emulsion Powder being obtained has good powder fluidity, redispersibility and film property.Due to emulsion
It is simultaneously introduced internal plasticization monomer and cross-linking monomer, the propylene that the resistance to water of redispersion sol film is more common can be again in building-up process
The 24h resistance to water of dispersed latex is greatly improved, and water absorption rate is 2.0%.
Embodiment 3
The composition of acrylate polymer emulsion include ethyl methacrylate, propyl methacrylate, ethyl acrylate,
Butyl acrylate, acrylic acid 5 hydroxyl pentyl ester, methacrylic acid, n, n' methylene-bisacrylamide, maleic hydrazide, its
Concrete component formula such as table 3 below:
Table 3
The manufacture method of acrylate polymer emulsion, its step is as follows:
A, by the ethyl methacrylate of above-mentioned mass parts, propyl methacrylate, ethyl acrylate, butyl acrylate,
Acrylic acid 5 hydroxyl pentyl ester, methacrylic acid, n, n' methylene-bisacrylamide, maleic hydrazide are mixed mixed respectively
Close monomer and mix monomer.According to fox formula, wherein mix monomer forms 23.2 DEG C of the tg=of copolymer, mix monomer
Tg=65.7 DEG C of composition copolymer.
B, preparation seed emulsion: the water of water gross mass 80% will be accounted for, the emulsifying agent accounting for total emulsifiers quality 60% draws with accounting for
The initiator sending out agent quality 450% is added in reactor, and dispersed with stirring 20 minutes treats that temperature rises to 85 DEG C, by 15% mass
Mix monomer in 30 minutes instillation reactors, after completion of dropping be incubated 25 minutes, prepared seed emulsion；
C, in 1.5 hours, 75% mix monomer is uniformly added drop-wise in the seed emulsion that step b obtains, completion of dropping
React 15 minutes afterwards；Then remaining mix monomer and 10% mix monomer ii are uniformly mixed into mix monomer iii, and
In 75 minutes, mix monomer iii is uniformly added drop-wise in above-mentioned emulsion, reacts 30 minutes after completion of dropping；Followed by will be remaining
Mix monomer ii was uniformly added drop-wise in above-mentioned emulsion in 2 hours；Remaining water, emulsifying agent and initiator while Deca monomer
Continuously it is added drop-wise in the seed emulsion that b step obtains, reacts 1 hour after completion of dropping, then be warming up to 90 DEG C and be incubated 1 hour, so
After be cooled to 50 DEG C, filtering and discharging, obtain final product acrylate polymer emulsion.
The mean diameter testing the propylene polymer emulsion obtaining is 102nm, propylene polymer emulsion powder redispersion
The particle diameter of liquid is 115nm；The former emulsion of tem analysis shows becomes of uniform size spherical with the latex particle of redispersion liquid, but divides again
The particle diameter of dispersion liquid is larger；Sem and Atomic Mechanics microscope (afm) analysis shows redispersion sol film are all had with former emulsion film
Good filming performance, and no phenomenon of phase separation；The minimum film formation temperature of former emulsion is 2 DEG C, the minimum film forming of redispersion liquid
Temperature is 3 DEG C；Nuclear magnetic resonance, NMR (nmr) analysis shows be obtained propylene polymer emulsion composition from micelle center to surface by
Gradual change.
Under conditions of being spray-dried, prepared Redispersible Polymeric Emulsion Powder has higher yield, reaches more than 98%,
And the Redispersible Polymeric Emulsion Powder being obtained has good powder fluidity, redispersibility and film property.Due to emulsion
It is simultaneously introduced internal plasticization monomer and cross-linking monomer, the propylene that the resistance to water of redispersion sol film is more common can be again in building-up process
The 24h resistance to water of dispersed latex improves a lot, and water absorption rate is 2.5%.
Embodiment 4:
The composition of acrylate polymer emulsion include methyl methacrylate, ethyl methacrylate, acrylic acid methyl ester.,
Butyl acrylate, acrylic acid 2 hydroxy methacrylate, methacrylic acid, acrylic acid, Methacrylamide, n, n' diacetyl hydrazine and oneself
Two hydrazides, its concrete component formula such as table 4 below:
Table 4
The manufacture method of acrylate polymer emulsion, its step is as follows:
A, by the methyl methacrylate of above-mentioned mass parts, ethyl methacrylate, acrylic acid methyl ester., butyl acrylate,
Acrylic acid 2 hydroxy methacrylate, methacrylic acid, acrylic acid, Methacrylamide, n, n' diacetyl hydrazine and adipic dihydrazide are respectively
It is mixed and made into mix monomer and mix monomer.According to fox formula, wherein mix monomer forms the tg=24.5 of copolymer
DEG C, mix monomer forms tg=66.7 DEG C of copolymer.
B, preparation seed emulsion: the water of water gross mass 60% will be accounted for, the emulsifying agent accounting for total emulsifiers quality 40% draws with accounting for
The initiator sending out agent quality 40% is added in reactor, and dispersed with stirring 10 minutes treats that temperature rises to 78 DEG C, by 5% mass
Mix monomer, in 15 minutes instillation reactors, is incubated 15 minutes after completion of dropping, prepared seed emulsion；
C, in 1.5 hours, 85% mix monomer is uniformly added drop-wise in the seed emulsion that step b obtains, completion of dropping
React 15 minutes afterwards；Then remaining mix monomer and 15% mix monomer ii are uniformly mixed into mix monomer iii, and
In 50 minutes, mix monomer iii is uniformly added drop-wise in above-mentioned emulsion, reacts 15 minutes after completion of dropping；Followed by will be remaining
Mix monomer ii was uniformly added drop-wise in above-mentioned emulsion in 1.5 hours；Remaining water, emulsifying agent and initiation while Deca monomer
Agent is continuously added drop-wise in the seed emulsion that b step obtains, and reacts 0.5 hour after completion of dropping, then it is little to be warming up to 80 DEG C of insulations 1
When, then it is cooled to 40 DEG C, filtering and discharging, obtain final product acrylate polymer emulsion.
The mean diameter testing the propylene polymer emulsion obtaining is 109nm, propylene polymer emulsion powder redispersion
The particle diameter of liquid is 122nm；The former emulsion of tem analysis shows becomes of uniform size spherical with the latex particle of redispersion liquid, but divides again
The particle diameter of dispersion liquid is larger；Sem and Atomic Mechanics microscope (afm) analysis shows redispersion sol film are all had with former emulsion film
Good filming performance, and no phenomenon of phase separation；The minimum film formation temperature of former emulsion is 5 DEG C, the minimum film forming of redispersion liquid
Temperature is 0 DEG C；Nuclear magnetic resonance, NMR (nmr) analysis shows be obtained propylene polymer emulsion composition from micelle center to surface by
Gradual change.
Under conditions of being spray-dried, prepared Redispersible Polymeric Emulsion Powder has higher yield, reaches more than 98%,
And the Redispersible Polymeric Emulsion Powder being obtained has good powder fluidity, redispersibility and film property.Due to emulsion
It is simultaneously introduced internal plasticization monomer and cross-linking monomer, the 24h water absorption rate of redispersion sol film is 2.4% in building-up process.
Embodiment 5:
The composition of acrylate polymer emulsion includes methyl methacrylate, Isooctyl acrylate monomer, acrylic acid 3 hydroxyl
Propyl ester, methacrylic acid, n n-methylolacrylamide, sebacic dihydrazide, its concrete component formula such as table 5 below:
Table 5
The manufacture method of acrylate polymer emulsion, its step is as follows:
A, by the methyl methacrylate of above-mentioned quality, Isooctyl acrylate monomer, acrylic acid 3 hydroxy propyl ester, metering system
Acid, n n-methylolacrylamide, sebacic dihydrazide are mixed and made into mix monomer and mix monomer respectively.Public according to fox
Formula, wherein mix monomer form 19.7 DEG C of the tg=of copolymer, and mix monomer forms tg=54.7 DEG C of copolymer.
B, preparation seed emulsion: the water of water gross mass 70% will be accounted for, the emulsifying agent accounting for total emulsifiers quality 50% draws with accounting for
The initiator sending out agent quality 45% is added in reactor, and dispersed with stirring 10 minutes treats that temperature rises to 80 DEG C, by 10% mass
Mix monomer, in 20 minutes instillation reactors, is incubated 20 minutes after completion of dropping, prepared seed emulsion；
C, in 2 hours, 70% mix monomer is uniformly added drop-wise in the seed emulsion that step b obtains, after completion of dropping
Reaction 25 minutes；Then remaining mix monomer and 15% mix monomer ii are uniformly mixed into mix monomer iii, and 70
In minute, mix monomer iii is uniformly added drop-wise in above-mentioned emulsion, reacts 30 minutes after completion of dropping；Followed by will be remaining mixed
Close monomer ii to be uniformly added drop-wise in above-mentioned emulsion in 1.5 hours；Remaining water, emulsifying agent and initiator while Deca monomer
Continuously it is added drop-wise in the seed emulsion that b step obtains, reacts 0.5 hour after completion of dropping, then be warming up to 85 DEG C and be incubated 1 hour,
Then it is cooled to 50 DEG C, filtering and discharging, obtain final product acrylate polymer emulsion.
The mean diameter testing the propylene polymer emulsion obtaining is 110nm, propylene polymer emulsion powder redispersion
The particle diameter of liquid is 126nm；The former emulsion of tem analysis shows becomes of uniform size spherical with the latex particle of redispersion liquid, but divides again
The particle diameter of dispersion liquid is larger；Sem and Atomic Mechanics microscope (afm) analysis shows redispersion sol film are all had with former emulsion film
Good filming performance, and no phenomenon of phase separation；The minimum film formation temperature of former emulsion is 2 DEG C, the minimum film forming of redispersion liquid
Temperature is 4 DEG C；The composition of propylene polymer emulsion that nuclear magnetic resonance, NMR (nmr) analysis shows are obtained from micelle center to surface is in
Gradually change.
Under conditions of being spray-dried, prepared Redispersible Polymeric Emulsion Powder has higher yield, reaches more than 97%,
And the Redispersible Polymeric Emulsion Powder being obtained has good powder fluidity, redispersibility and film property.Due to emulsion
It is simultaneously introduced internal plasticization monomer and cross-linking monomer, the propylene that the resistance to water of redispersion sol film is more common can be again in building-up process
The 24h resistance to water of dispersed latex is greatly improved, and water absorption rate is only 1.65%.
Embodiment 6:
It is different pungent that the composition of acrylate polymer emulsion includes methyl methacrylate, ethyl methacrylate, acrylic acid
Ester, acrylic acid methyl ester., butyl acrylate, acrylic acid 2 hydroxy methacrylate, the own ester of acrylic acid 6 hydroxyl, methacrylic acid, propylene
Acid, Methacrylamide, maleic hydrazide and adipic dihydrazide, its concrete component formula such as table 6 below:
Table 6
The manufacture method of acrylate polymer emulsion, its step is as follows:
A, by the methyl methacrylate of above-mentioned mass parts, ethyl methacrylate, Isooctyl acrylate monomer, acrylic acid first
Ester, butyl acrylate, acrylic acid 2 hydroxy methacrylate, the own ester of acrylic acid 6 hydroxyl, methacrylic acid, acrylic acid, metering system
Amide, maleic hydrazide and adipic dihydrazide are mixed and made into mix monomer and mix monomer respectively.
B, preparation seed emulsion: the water of water gross mass 60% will be accounted for, the emulsifying agent accounting for total emulsifiers quality 40% draws with accounting for
The initiator sending out agent quality 40% is added in reactor, and dispersed with stirring 15 minutes treats that temperature rises to 80 DEG C, by 10% mass
Mix monomer, in 20 minutes instillation reactors, is incubated 30 minutes after completion of dropping, prepared seed emulsion；
C, in 2 hours, 75% mix monomer is uniformly added drop-wise in the seed emulsion that step b obtains, after completion of dropping
Reaction 20 minutes；Then remaining mix monomer and 20% mix monomer ii are uniformly mixed into mix monomer iii, and 70
In minute, mix monomer iii is uniformly added drop-wise in above-mentioned emulsion, reacts 25 minutes after completion of dropping；Followed by will be remaining mixed
Close monomer ii to be uniformly added drop-wise in above-mentioned emulsion in 2 hours；While Deca monomer, remaining water, emulsifying agent and initiator connect
Continue and be added drop-wise in the seed emulsion that b step obtains, react 1 hour after completion of dropping, then be warming up to 90 DEG C and be incubated 1 hour, then
It is cooled to 50 DEG C, filtering and discharging, obtain final product acrylate polymer emulsion.
The mean diameter testing the propylene polymer emulsion obtaining is 112nm, propylene polymer emulsion powder redispersion
The particle diameter of liquid is 126nm；The former emulsion of tem analysis shows becomes of uniform size spherical with the latex particle of redispersion liquid, but divides again
The particle diameter of dispersion liquid is larger；Sem and Atomic Mechanics microscope (afm) analysis shows redispersion sol film are all had with former emulsion film
Good filming performance, and no phenomenon of phase separation；The minimum film formation temperature of former emulsion is 3 DEG C, the minimum film forming of redispersion liquid
Temperature is 0 DEG C；Nuclear magnetic resonance, NMR (nmr) analysis shows be obtained propylene polymer emulsion composition from micelle center to surface by
Gradual change.
Be spray-dried under conditions of, prepared Redispersible Polymeric Emulsion Powder has higher yield, reach 98.5% with
On, and the Redispersible Polymeric Emulsion Powder being obtained has good powder fluidity, redispersibility and film property.Due to breast
It is simultaneously introduced internal plasticization monomer and cross-linking monomer, the propylene that the resistance to water of redispersion sol film is more common can in liquid building-up process
The 24h resistance to water of redispersion latex is greatly improved, and water absorption rate is 1.4%.
It should be noted that embodiments of the present invention being not restricted to the described embodiments, other any without departing from
The spirit of the present invention and the change made under principle, modification, replacement, combine, simplify, all should be equivalent substitute mode,
It is included within protection scope of the present invention.
Claims (9)
1. a kind of acrylate polymer emulsion is it is characterised in that be made up of the raw material components of following mass percent:
Described initiator is persulfuric acid salt initiator；
Described emulsifying agent is anion emulsifier and nonionic emulsifier compounds；Anionic and nonionic mass ratio be 1～
3:1, anion emulsifier is in dodecly diphenyl ether sulfonate disodium, dodecylbenzene sodium sulfonate and sodium lauryl sulphate
One or more；Nonionic emulsifier is polysorbas20, Tween 80, polyoxyethylene Zhong Xin 2, 2-Oxydiphenol 10 and NPE
One or more of；
Described alkyl methacrylate is methyl methacrylate, ethyl methacrylate, propyl methacrylate, methyl-prop
One or more of olefin(e) acid butyl ester, pentylmethacrylate, N-Hexyl methacrylate and 2-Propenoic acid, 2-methyl-, isooctyl ester；
Described alkyl acrylate be acrylic acid methyl ester., ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate,
One or more of Hexyl 2-propenoate and Isooctyl acrylate monomer；
Described hydroxy alkyl ester is acrylic acid 2 hydroxy methacrylate, acrylic acid 3 hydroxy propyl ester, acrylic acid 2 hydroxybutyl, propylene
Sour 5 hydroxyl pentyl esters, the own ester of acrylic acid 6 hydroxyl, methacrylic acid 2 hydroxy methacrylate and methacrylic acid 3 hydroxy propyl ester
One or more of；
Described alkyl carboxylic acid is methacrylic acid and/or acrylic acid；Described acrylic amide is acrylamide, methacryl
Amine, n, one or more of n' methylene-bisacrylamide, n n-methylolacrylamide and n N-isopropylacrylamide；Institute
Stating hydrazides is unifor, n, in n' diacetyl hydrazine, maleic hydrazide, adipic dihydrazide and sebacic dihydrazide
Plant or multiple；
The step including during preparation is as follows:
A, by percentage to the quality, first by 10%～50% alkyl methacrylate in composition of raw materials, 50%～90%
The acrylic amide of alkyl acrylate, 0～30% hydroxy alkyl ester, 0～30% alkyl carboxylic acid and 0～30% is mixed
Mix monomer；Again by remaining for formula ratio alkyl methacrylate, alkyl acrylate, hydroxy alkyl ester, alkyl carboxylic acid and third
Eneamide is mixed and made into mix monomer；Mix monomer is controlled to be 1.5～3:1 with the mass ratio of mix monomer；Control mixed
Close the polymers obtained vitrification point of monomer and be less than the polymers obtained vitrification point of mix monomer；
B, preparation seed emulsion: the water of water gross mass 60%～80% will be accounted for, account for the emulsifying of total emulsifiers quality 40%～60%
Agent and account for the initiator of initiator quality 40%～50% and be added in reactor, dispersed with stirring, treat that temperature rises to 78～85 DEG C,
The mix monomer of 5%～15% mass is instilled in reactor, is incubated 15～30 minutes after completion of dropping, prepared seed emulsion；
C, by percentage to the quality, 75%～85% mix monomer is uniformly added drop-wise in the seed emulsion that step b obtains, and drips
Add and react 15～30 minutes after finishing；Then remaining mix monomer and 10%～20% mix monomer ii are uniformly mixed into
Mix monomer iii, mix monomer iii is uniformly added drop-wise in emulsion, reacts 15～30 minutes after completion of dropping；Remaining mixing is single
Body ii is uniformly added drop-wise in described emulsion；While Deca monomer, remaining water, emulsifying agent and initiator are continuously added drop-wise to b step
Suddenly in the seed emulsion obtaining, react 0.5～1 hour after completion of dropping, then be warming up to 80～90 DEG C and be incubated 0.5～1 hour, so
After be cooled to 40～50 DEG C, obtain product；
Described hydrazides is used in mix monomer, or described hydrazides is used in mix monomer and mix monomer.
2. acrylate polymer emulsion according to claim 1 is it is characterised in that described persulfuric acid salt initiator is
One or more of potassium peroxydisulfate, sodium peroxydisulfate and Ammonium persulfate..
3. acrylate polymer emulsion according to claim 1 or claim 2 preparation method it is characterised in that include step
As follows:
A, by percentage to the quality, first by 10%～50% alkyl methacrylate in composition of raw materials, 50%～90%
The acrylic amide of alkyl acrylate, 0～30% hydroxy alkyl ester, 0～30% alkyl carboxylic acid and 0～30% is mixed
Mix monomer；Again by remaining for formula ratio alkyl methacrylate, alkyl acrylate, hydroxy alkyl ester, alkyl carboxylic acid and third
Eneamide is mixed and made into mix monomer；Mix monomer is controlled to be 1.5～3:1 with the mass ratio of mix monomer；Control mixed
Close the polymers obtained vitrification point of monomer and be less than the polymers obtained vitrification point of mix monomer；
B, preparation seed emulsion: the water of water gross mass 60%～80% will be accounted for, account for the emulsifying of total emulsifiers quality 40%～60%
Agent and account for the initiator of initiator quality 40%～50% and be added in reactor, dispersed with stirring, treat that temperature rises to 78～85 DEG C,
The mix monomer of 5%～15% mass is instilled in reactor, is incubated 15～30 minutes after completion of dropping, prepared seed emulsion；
C, by percentage to the quality, 75%～85% mix monomer is uniformly added drop-wise in the seed emulsion that step b obtains, and drips
Add and react 15～30 minutes after finishing；Then remaining mix monomer and 10%～20% mix monomer ii are uniformly mixed into
Mix monomer iii, mix monomer iii is uniformly added drop-wise in emulsion, reacts 15～30 minutes after completion of dropping；Remaining mixing is single
Body ii is uniformly added drop-wise in described emulsion；While Deca monomer, remaining water, emulsifying agent and initiator are continuously added drop-wise to b
In the seed emulsion that step obtains, react 0.5～1 hour after completion of dropping, then be warming up to 80～90 DEG C and be incubated 0.5～1 hour,
Then it is cooled to 40～50 DEG C, obtain product.
4. the preparation method of acrylate polymer emulsion according to claim 3 is it is characterised in that described mix monomer
Iii was uniformly added drop-wise in emulsion in 50～75 minutes；Remaining mix monomer ii was uniformly added drop-wise to institute in 1.5～2 hours
State in emulsion.
5. the preparation method of acrylate polymer emulsion according to claim 3 is it is characterised in that described initiator
Consumption is the 0.5%～1.0% of all monomer gross mass；Described emulsifier be all monomer gross mass 1.0%～
1.5%.
6. the preparation method of acrylate polymer emulsion according to claim 3 is it is characterised in that described mix monomer
Polymer glass temperature tg of preparation is 40～20 DEG C, and the polymer glass temperature of described mix monomer preparation is
40～75 DEG C.
7. the preparation method of acrylate polymer emulsion according to claim 3 is it is characterised in that stir described in step b
Mix the scattered time for 10～20 minutes.
8. the preparation method of acrylate polymer emulsion according to claim 3 is it is characterised in that mix described in step b
Close monomer in 15～30 minutes instillation reactors.
9. the preparation method of acrylate polymer emulsion according to claim 3 is it is characterised in that described in step c
75%～85% mix monomer was uniformly added drop-wise in the seed emulsion that step b obtains in 1.5～2 hours.
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