CN1743352A - Polyurethane and its complex substance in-situ modified polyvinyl chloride resin and preparing method - Google Patents
Polyurethane and its complex substance in-situ modified polyvinyl chloride resin and preparing method Download PDFInfo
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- CN1743352A CN1743352A CN 200510015285 CN200510015285A CN1743352A CN 1743352 A CN1743352 A CN 1743352A CN 200510015285 CN200510015285 CN 200510015285 CN 200510015285 A CN200510015285 A CN 200510015285A CN 1743352 A CN1743352 A CN 1743352A
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Abstract
This invention relates to a polyurethane and its complex in situ modified PVC resin and preparing method, mainly overcoming dispersion inhomogeneity and mixing time influence on resin property during existing physical-mechanical mixing. This invention comprises: using polyurethane as seed, by intermittent or semi-continuous charging mode,making polyurethane-acrylic ester composite emulsion with nucleocapsid structure, then under existence of said composite latex, adding chloroethylene monomer to autoclave to emulsion(suspension) polymerizing, obtaining new-type PVC composite resin, as to form hydrogen bond combining carbamate base hydrogen atom of polyurethane elastomer component with mass polar choloride atom of PVC macromolecular chain,so as to increase both compatibility ,and to improve processability of PVC.This invention develops new process of polyurethane modified PVC,increases PVC notch impact stength, in particular weathering resistance in cold area, can be used for building materials, and widens PVC application range.
Description
Technical field
The present invention relates to a kind of preparation method of modified polyvinyl chloride compound resin, particularly a kind of new polyurethane and complex substance in-situ modified polyvinyl chloride resin thereof and preparation method thereof.
Background technology
Polyvinyl chloride (PVC) is as one of Application and Development large general-purpose plastics kind the earliest, be widely used in every field because of having over-all propertieies such as good rigidity, erosion resistance, electric insulating quality and cheap price, its output is only second to polyolefine and occupy second.At present, the PVC that mainly produces of industrial widespread usage by suspension and emulsion method.The former generally is used to make boardy product, and the latter is mainly used in the manufacturing of coating, leatheroid, tackiness agent etc.Yet polyvinyl chloride also exists shortcomings such as impact property is poor, thermostability is low, processing characteristics is bad, therefore on range of application, especially is very restricted as structured material and engineering plastics application.The method of modifying of polyvinyl chloride mainly is by (grafting) copolymerization chemical modification and physical blending modification, and researcher has carried out big quantity research to the modification, particularly toughening modifying of PVC both at home and abroad, mainly concentrates on elastomerics and softening agent modification aspect.For example chlorinatedpolyethylene (CPE), core-shell type polyacrylic ester (ACR) or softening agent are mixed the blending and modifying that carries out among the PVC.For elastomer blended modifier, exist rubber phase and disperse the problem uneven, that modification efficiency is low, simultaneously low by the PVC material at low temperature notched Izod impact strength of nuclear-shell ACR modification, this material is restricted in the use of the open air of cold district; For the modification of softening agent, often exist softening agent and easily ooze out, material modulus is descended the degradation shortcoming significantly.It is VC suspension grafting (ACR-g-VC) under the ACR emulsion exists that relevant grafting rubbers vinylchlorid (VC) is studied maximum at present.
By the macromolecular material of compound different structure of certain way and performance, make it to have complementary advantages, be one of method commonly used in the new material development.Urethane (PU) is a kind of segmented copolymer, is made up of unformed soft segment and crystallizable hard block.Polyethers or polyester are soft section, and a little less than the polarity, the external phase of its constituent material is given PU elasticity and controlled lower temperature resistance, solvent resistance and the weathering resistance of PU.The segment that vulcabond and chainextender reaction generate is hard section, and polarity is strong, is controlling intensity and the thermotolerance of PU.The rerum natura of the existing rubber of urethane such as good springiness, wear-resisting and oil resistant, has the processing of plastic performance again, and the disadvantage of PVC is that thermostability and shock resistance are poor, especially low-temperature impact resistance, thereby limited its application under some severe environment, the shortcoming that can overcome the two effectively that combines of polyvinyl chloride and urethane.At present, polyvinyl chloride and polyurethane comixing research are more, in urethane and polyvinyl chloride direct mechanical blending and modifying technology, the degree of scatter of urethane and polyvinyl chloride and blending temperature are bigger for the resin property influence: to polyvinyl chloride, because it is responsive to temperature, therefore easily degrade, will reduce the decomposition of polyvinyl chloride as far as possible and reduce processing temperature.But temperature reduces, and mixes inequality between the material, having caking to produce, and plasticizing rate is not high, is difficult to form finely dispersed structure, and is serious to the influence of blend mechanical property.The PU-g-VC multipolymer that obtains by the grafted method has flame retardant resistance, the processibility of good wear-resisting, the oil resistant of PU, performance such as cold-resistant and PVC.Graft copolymer just has the characteristic of soft pvc under the situation that does not add softening agent, thereby does not have phenomenons such as small molecules plasticizer exudation, volatilization and migration.
Summary of the invention
The technical problem that solves:
The invention provides a kind of Polyurethane and Composite Normal Position Modify Pvc Resin and Preparation Method.The present invention breaks through traditional mechanical blending process, and a kind of method of chemical graft copolymerization polychloroethylene compound resin is provided, and adopts aqueous polyurethane emulsion and vinylchlorid graft copolymerization, forms the PU-g-VC compound resin.Utilize polyurethane elastomer softness, wear-resisting, purpose that adhesivity reaches effective toughening PVC well.But single PU emulsion also has the place of some shortcomings in stability, from aspects such as thickening property, solid content, ranges of application; Toughness, wear resistance, water tolerance and the chemical proofing of comparing pure polyacrylate dispersion (PA) with the PU emulsion are relatively poor, if with PA PU is carried out modification, can make both performances obtain complementation.Core-shell type polyurethane-acrylate (PUA) composite emulsion can overcome shortcoming separately, and performance advantage separately is significantly improved the character of emulsion and glued membrane.The stable emulsion and the vinylchlorid grafting of the excellent combination property that the present invention obtains the two combination are used for the modification of polyvinyl chloride, have developed the novel process of polyurethane-modified polyvinyl chloride.
The technical scheme that solve the technical problem is:
A kind of urethane and complex substance in-situ modified polyvinyl chloride resin thereof, it is to prepare according to the following steps:
(1) preparation of hud typed compounded latex particle
A. Synthesis of Waterborne Polyurethane
The composition quality umber
Polyvalent alcohol 100
Isocyanic ester 20.31～31.68
Terminal hydroxy group carboxylic acid 4.48～8.96
Dibutyl tin laurate 0.000～0.002
Solvent 10～20
Thinner 10～20
Salt forming agent 3.0～6.0
Chainextender 0.0～3.0
Dispersion agent 350～400
Polyvalent alcohol refers to polyester diol (PPG), polyether Glycols and composition thereof; Solvent and thinner refer to acetone, methylethylketone, dioxane, N respectively, dinethylformamide, N-Methyl pyrrolidone or toluene; Salt forming agent refers to sodium hydroxide, ammoniacal liquor or triethylamine, and degree of neutralization is 60～100%; Chainextender refers to 1, one or more in 4-butyleneglycol, ethylene glycol, glycol ether, ethylene glycol or the TriMethylolPropane(TMP);
Above-mentioned each reactant is all carried out processed before use, polyvalent alcohol and isocyanic ester stirring reaction 1～2 hour in 60～100 ℃ of scopes, add the terminal hydroxy group carboxylic acid that has been dissolved in advance in the solvent then and continue reaction 0.5～2 hour, be cooled to 50 ℃ afterwards, add thinner and reduce viscosity, add salt forming agent again and neutralize, react after 30 minutes, add chainextender and dispersion agent high-speed stirring, dispersion and emulsion, make the self-emulsifying anion-type water-thinned polyurethane;
B. the preparation of polyurethane-acrylate composite emulsion
The composition quality umber
Self-control aqueous polyurethane 50～100
Acrylate monomer 0.0～15.3
Deionized water 32.14～45.92
Linking agent 0.0～2.6
Emulsifying agent 0.0～1.3
Initiator 0.26～1.32
Acrylate monomer refers to other acrylate of butyl acrylate (BA), 2-EHA (EHA) or second-order transition temperature Tg＜-10 ℃ and their mixture, and initiator is Potassium Persulphate (K
2S
2O
4); Emulsifying agent is selected sodium lauryl sulphate (SDS) for use; The mass ratio of urethane and polyacrylic ester is 40～100: 0～60 in the compounded latex of gained;
Under nitrogen protection, stirred 30 minutes under self-control aqueous polyurethane, deionized water and the emulsifier mix room temperature that will obtain by a step, make it fully emulsified, be warming up to 70～85 ℃ and add initiator down, dropwise addition of acrylic acid ester monomer and linking agent dropwised in 0.5～2 hour simultaneously, continued insulation reaction 1～3 hour, cooling discharge makes the polyurethane-acrylate compounded latex then;
(2) graft polymerization of vinyl chloride monomer and compounded latex
Wherein a kind of emulsion that step a or b are made joins in the autoclave, adds other component successively simultaneously, reacts under 0.4～0.9MPa;
Graft polymerization reaction adopts the mixed solution composition and the consumption of letex polymerization as follows:
The composition quality umber
Vinyl chloride monomer 100
Deionized water 200～300
Emulsifying agent 0.3～1.0
Initiator 0.3～3.0
Compounded latex 20～400
PH regulator agent 1～10
Initiator is Potassium Persulphate (K
2S
2O
4); Emulsifying agent is selected sodium lauryl sulphate (SDS) for use; The pH regulator agent is ten water Sodium Tetraboratees, sodium bicarbonate, sodium hydroxide or yellow soda ash; The mass ratio of urethane and polyacrylic ester is 40～100: 0～60 in the last step reaction gained compounded latex, and the pH regulator agent is ten water Sodium Tetraboratees, sodium bicarbonate, sodium hydroxide or yellow soda ash, and concentration is 0.5～15%, and the pH scope is 6～12;
Reaction system is airtight, vacuumize, fill nitrogen, exhaust, after the repetitive operation three times, adopt the reinforced vinyl chloride monomer that adds in continuous charging or disposable gap, after 8～16 hours, the fast cooling termination reaction is removed unreacted vinyl chloride monomer in 40～60 ℃ of following polymerizations, discharging sampling, prepared polyvinyl chloride graft polymkeric substance is freezing, breakdown of emulsion, filtration, washing, dry novel polyvinyl chloride emulsion resin.
Perhaps the emulsion polymerization of graft polymerization reaction employing is substituted by suspension polymerization,
The composition and the consumption of suspension polymerization mixed solution are as follows:
The composition quality umber
Vinyl chloride monomer 100
Deionized water 100～200
Dispersion agent 0.1～2.0/10～30
Initiator 0.2～1.0
Compounded latex 20～100
PH regulator agent 1～8
Wherein dispersion agent is polyvinyl alcohol (PVA, KH-20) and the compound system of Vltra tears (HPMC), initiator is the two 2-ethylhexyls (EHP) of peroxy dicarbonate, bicarbonate of ammonia is selected in the pH regulator agent for use, concentration is 10%, reaction system is airtight, vacuumize, fill nitrogen, after the exhaust, repetitive operation three times, adopt the reinforced vinyl chloride monomer that adds in continuous charging or disposable gap, in 40～60 ℃ of following polymerizations after 8～16 hours, the fast cooling termination reaction is removed unreacted vinyl chloride monomer, the discharging sampling, with prepared polyvinyl chloride graft polymkeric substance, filter, washing, dry novel polyvinyl chloride suspending resin.
The described isocyanic ester of step a is aromatic isocyanate or aliphatic isocyanates in the preparation process of above-mentioned urethane and complex substance in-situ modified polyvinyl chloride resin thereof, aromatic isocyanate is tolylene diisocyanate (TDI), ditan-4-4 '-vulcabond (MDI), liquefied mdi or poly methylene poly phenyl poly isocyanate (PAPI), aliphatic isocyanates is hexamethylene diisocyanate (HDI) or isoflurane chalcone diisocyanate (IPDT).
The described terminal hydroxy group carboxylic acid of step a is self-emulsifying chainextender, dimethylol propionic acid (DMPA) or contains the carboxyl half ester in the preparation process of above-mentioned urethane and complex substance in-situ modified polyvinyl chloride resin thereof.
In the preparation process of above-mentioned urethane and complex substance in-situ modified polyvinyl chloride resin thereof in the preparation of polyurethane-acrylate composite emulsion b, described linking agent refers to one or more the blend in allyl methacrylate(AMA), 1,4 butanediol diacrylate, allyl acrylate, Viscoat 295, diethylene glycol diacrylate, Vinylstyrene, Phthalic acid, diallyl ester, ethoxylated trimethylolpropane triacrylate, ethoxylated neopentylglycol double methacrylate and the homologue thereof.
In the preparation of polyurethane-acrylate composite emulsion b, dosage of crosslinking agent is respectively 0.5～5% of amount of monomer in the preparation process of above-mentioned urethane and complex substance in-situ modified polyvinyl chloride resin thereof.
Beneficial effect
The present invention is to be initial latex with PU, PU, PA are organically combined the stable PUA latex grafting vinylchlorid of the excellent combination property that obtains, be used for the modification of polyvinyl chloride, amino hydrogen atom and matrix PVC molecular chain Semi-polarity chlorine atom formation hydrogen bond in the polyurethane molecular structure have been utilized, strengthen the bonding force between the two-phase, improve the consistency of the two, reduce melt temperature, thereby improve the processing characteristics of PVC; Utilize in the polyurethane molecular structure soft section changeable and designability with hard section, carry out the overall design of PUA, improve the toughness and the over-all properties of compound resin, as satisfactory stability, for grafting, copolymerization and modification vinylchlorid provides condition.The present invention has developed the novel process of urethane and mixture modified polyvinyl chloride thereof, and 2～10 times (notched Izod impact strength of pure emulsion PVC is 2～3KJ/m to have improved the notched Izod impact strength of polyvinyl chloride
2), especially in the weathering resistance of cold district.Because it is nontoxic, free from environmental pollution that the polyurethane-acrylate compounded latex has, the compound resin of itself and vinylchlorid grafting gained is used for coating, tackiness agent or plastics all will helps environment protection greatly.The modified polyvinyl chloride compounded latex of the present invention's preparation can be widely used in fields such as chemical industry, building materials, has expanded the range of application of polyvinyl chloride, will produce very big economic and social benefit once applying.As seen, the graft polymerization compound resin of aqueous polyurethane and vinylchlorid obviously has great application prospect.
Embodiment
Embodiment 1:
(1) Synthesis of Waterborne Polyurethane
In the four-hole bottle that reflux exchanger and stirring are housed, add the 100g polyoxytrimethylene alcohol of processed, stir logical nitrogen and water of condensation, heat temperature raising, when treating that temperature rises to 70 ℃, add 31.68g tolylene diisocyanate and 1 catalyzer, after the system heat release was stable, 70 ℃ were reacted 1 hour.Add 5.36g terminal hydroxy group carboxylic acid (dimethylol propionic acid) afterwards, be dissolved in the 14g solvent (N, dinethylformamide), 70 ℃ are continued reaction down.1.5 after hour, cool to 50 ℃, add 13.86g thinner (acetone) and reduce system viscosity, be beneficial to the dispersion of performed polymer, Dropwise 5 .22g salt forming agent (triethylamine) simultaneously, in and carboxyl, dropwised in about 10 minutes, continue reaction 0.5 hour afterwards.Finish reaction, obtain base polyurethane prepolymer for use as.This performed polymer is transferred in another container, drip 1 under room temperature, 4-butyleneglycol 0.9g chain extension adds 382.14g dispersion agent (deionized water) again, high-speed stirring, shearing, emulsification 1～2 hour finally obtain solid content and are 20～30% self-emulsifying anion aqueous polyurethane.
(2) preparation of polyurethane-acrylate compounded latex
In the four-hole bottle that reflux exchanger and stirring are housed, add 245g self-control water-soluble polyurethane latex, 0.26g sodium lauryl sulphate (SDS) and 78.75g deionized water, stirred 30 minutes under the room temperature, make it fully emulsified, logical nitrogen and water of condensation.Warming-in-water to 78 ℃ adds 0.79g Potassium Persulphate (K
2S
2O
4) (being dissolved in the 25ml deionized water), drip the mixture of 26.25g butyl acrylate and 0.39g allyl methacrylate(AMA) linking agent simultaneously, dropwised in about 1.5～2 hours.78 ℃ were continued insulation reaction 2 hours down, finished reaction, and cooling discharge obtains the polyurethane-acrylate compounded latex.
(3) polychloroethylene compound resin (PUA-g-VC) is synthetic
The polyurethane-acrylate composite particles latex 80g that adds 900ml deionized water, 3.7g sodium lauryl sulphate, 2.9g Potassium Persulphate and solid content about 20% in the 2L stainless steel autoclave that stirring, charging opening, nitrogen inlet and pump drainage mouth are housed regulates the pH value of mixed reaction solution 9.5～10.5 with 15g 1%NaOH solution.Vacuumize, inflated with nitrogen, emptying, after the repetitive operation three times, add the 400g vinyl chloride monomer continuously and under room temperature, stir.Temperature reaction, controlled polymerization temperature be at 50 ± 0.5 ℃, pressure 0.7MPa.When question response still pressure reduces 0.2MPa, fast cooling, decompression removes unreacted vinyl chloride monomer, and discharging, sampling, are drying to obtain the polyvinyl chloride hybrid emulsion resins at the freezing breakdown of emulsion of all the other emulsions.
(4) preparation of Mechanics Performance Testing sample:
Press table 1 prescription, after resin that embodiment is made and various auxiliary agent prepare, be placed on and mix 10min. in the high-speed mixer.Mixing on twin-roll machine mixed material then, 165～170 ℃ of control roller temperature, the thin-pass number of times is 12 times, the about 1.1mm of slice thickness.With going out sheet material on request thickness overlay in the mould, preheating 10min in 175 ℃ of following hydropress is forced into 15MPa pressurize 4min., then is chilled to the room temperature slice under 12MPa, impacts and tensile bars usefulness for tailoring.
Table 1 vinylchlorid graft copolymerization resin treatment test raw material prescription
| Component polychloroethylene compound resin organotin calcium stearate stearyl alcohol |
| Mass ratio 100 2.5 0.8 0.8 |
Shock strength test: above-mentioned sheet coupon is cut into the notch shock batten by the GB/T1043-93 standard with omnipotent sampling machine, at least after placing 24h, newly think carefully on the ZBC-4 type charpy impact test machine that company limited produces in Shenzhen and to carry out shock test, probe temperature is 23 ℃.
The tensile property test: institute's panel is cut into the dumbbell shape tensile bars by the GB/T1040-92 standard, tests its tensile strength with RGT-10A type microcomputer control electronics universal testing machine down at 23 ℃, draw speed is 20mm/min..
According to the test method of GB-1633-79 softening temperature (dimension card), measure thermoplastics in liquid heat-transfer medium, at certain load, under certain constant heatingrate's condition, the temperature when sample is pressed into 1 millimeter by 1 millimeter 2 indentor point.Determining instrument is the thermal distortion of XWB-300F type, vicat softening point temperature determinator.
Embodiment 2:
In compounded latex (2) preparation process, add 360g self-control aqueous polyurethane, 10g butyl acrylate, allyl methacrylate(AMA) 0.1g, deionized water 30g, Potassium Persulphate 0.3g, sodium lauryl sulphate 0.3g, other experimentation is with embodiment 1.
Embodiment 3:
In compounded latex (2) preparation process, add 320g self-control aqueous polyurethane, 20g butyl acrylate, allyl methacrylate(AMA) 0.2g, deionized water 60g, Potassium Persulphate 0.6g, sodium lauryl sulphate 0.3g, other experimentation are together
Embodiment 1.
Embodiment 4:
In compounded latex (2) preparation process, add 210g self-control aqueous polyurethane, 35g butyl acrylate, allyl methacrylate(AMA) 0.35g, deionized water 105g, Potassium Persulphate 1.05g, sodium lauryl sulphate 0.3g, other experimentation is with embodiment 1.
Synthetic PUA/PVC emulsion resin and material property table look-up thereof among table 2 embodiment
| Embodiment number | Changing factor | Vicat softening point (℃) | Notched Izod impact strength (KJ/m 2) | Tensile strength (MPa) |
| 1 | PU/PA＝70/30 | 74.15 | 4.02 | 46.00 |
| 2 | PU/PA＝90/10 | 73.80 | 4.09 | 45.87 |
| 3 | PU/PA＝80/20 | 74.20 | 3.75 | 45.40 |
| 4 | PU/PA＝60/40 | 74.15 | 5.18 | 43.35 |
Annotate: among above each embodiment, the PUA latex content all accounts for 5.40% of hybrid emulsion resins quality.
Embodiment 5:
In the preparation of aqueous polyurethane (1), add the 100g polyoxytrimethylene alcohol of processed, the 31.68g toluene diisocyanate, 1 catalyzer, 5.36g terminal hydroxy group carboxylic acid (dimethylol propionic acid), 14g solvent (N, dinethylformamide), 5.22g triethylamine, the 396.75g deionized water does not add 1, the 4-butyleneglycol, directly add water-dispersion emulsification, preparation lower molecular weight aqueous polyurethane, other experimentation is with embodiment 1.
Embodiment 6:
In the preparation of aqueous polyurethane (1), add 100g polyoxytrimethylene alcohol, 31.68g tolylene diisocyanate, 1 catalyzer, 5.36g terminal hydroxy group carboxylic acid (dimethylol propionic acid), the 14g solvent (N of processed, dinethylformamide), 5.22g triethylamine, 0.61g1,4-butyleneglycol, 382.14g deionized water, other experimentation is with embodiment 1.
Embodiment 7:
In the preparation of aqueous polyurethane (1), add 1.35g1,4-butyleneglycol, 386.66g deionized water, other experimentation and raw material consumption are with embodiment 1.
Embodiment 8:
In the preparation of aqueous polyurethane (1), add 1.8g1,4-butyleneglycol, 380.95g deionized water, other experimentation and raw material consumption are with embodiment 1.
Embodiment 9:
In the preparation of aqueous polyurethane (1), add 2.25g1,4-butyleneglycol, the 380.50g deionized water, other process and raw material consumption are with embodiment 1.
Synthetic PUA/PVC emulsion resin and material property table look-up thereof among table 3 embodiment
| Embodiment number | Changing factor | Vicat softening point (℃) | Notched Izod impact strength (KJ/m 2) | Tensile strength (MPa) |
| 5 | M PU＝4700 | 74.15 | 4.02 | 46.00 |
| 6 | M PU＝6000 | 73.85 | 4.83 | 44.70 |
| 7 | M PU＝9500 | 72.60 | 5.35 | 49.38 |
| 8 | M PU＝14000 | 73.90 | 4.21 | 46.60 |
| 9 | M PU＝26000 | 72.00 | 4.64 | 46.57 |
Annotate: among above each embodiment, the PU/PA=70/30 of PUA latex, and PUA content all accounts for 5.14% of hybrid emulsion resins quality.
Embodiment 10:
In the preparation of compounded latex (2), add 245g self-control water-soluble polyurethane latex, 0.26g sodium lauryl sulphate, 78.75g deionized water, 0.79g Potassium Persulphate, 26.25g butyl acrylate, 0.39g allyl methacrylate(AMA), the Butyl Acrylate Monomer feed way changes into intermittently disposable reinforced, and other is operated with embodiment 1.
Embodiment 11:
In the preparation of compounded latex (2), experimentation and feeding quantity be with embodiment 1, and just to change pre-swelling method into reinforced for the monomer addition mode.
Synthetic PUA/PVC emulsion resin and material property table look-up thereof among table 4 embodiment
| Embodiment number | Changing factor | Notched Izod impact strength (KJ/m 2) | Tensile strength (MPa) |
| 1 | The seed semi-continuous charging | 38.50 | 38.72 |
| 10 | Intermittently reinforced | 36.84 | 38.10 |
| 11 | Pre-swelling is reinforced | 48.24 | 38.78 |
Annotate: among above each embodiment, the PU molecular weight is 7100, the PU/PA=70/30 of PUA latex, and PUA content all accounts for 5.66% of hybrid emulsion resins quality.
Embodiment 12:
In the preparation of aqueous polyurethane (1), add 100g polyoxytrimethylene alcohol, 31.68g tolylene diisocyanate, 1 catalyzer, 5.36g terminal hydroxy group carboxylic acid (dimethylol propionic acid), the 14g solvent (N of processed, dinethylformamide), 5.22g triethylamine, 386.66g deionized water, chainextender changes quadrol into, add-on is 0.3g, and other experimentation is with embodiment 1.
Embodiment 13:
In the preparation of aqueous polyurethane (1), chainextender changes glycol ether into, and add-on is 1.06g, and other experimentation and raw material consumption are with embodiment 1.
Embodiment 14:
In the preparation of aqueous polyurethane (1), chainextender changes ethylene glycol into, and add-on is 0.62g, and other experimentation and raw material consumption are with embodiment 1.
Embodiment 15:
In the preparation of aqueous polyurethane (1), chainextender changes glycerol into, and add-on is 0.61g, and other experimentation and raw material consumption are with embodiment 1.
Synthetic PUA/PVC emulsion resin and material property table look-up thereof among table 6 embodiment
| Embodiment number | Changing factor | Notched Izod impact strength (KJ/m 2) | Tensile strength (MPa) |
| 12 | Chainextender is a quadrol | 22.85 | 40.35 |
| 13 | Chainextender is a glycol ether | 56.54 | 39.91 |
| 14 | Chainextender is an ethylene glycol | 35.90 | 40.78 |
| 15 | Chainextender is a glycerol | 55.61 | 39.00 |
Annotate: among above each embodiment, the PU molecular weight is 7100, and other is with embodiment 1.
Embodiment 16:
Operating process is with embodiment 1, but synthetic (2) polyurethane-acrylate compounded latex, and directly uses the water-soluble polyurethane latex and the vinyl chloride monomer graft polymerization of step (1), implementation step (3), and the vinyl chloride monomer feed way is a continuous charging.Organotin changes calcium zinc stabilizer in the step (4), and consumption is 4 parts.
Embodiment 17:
Experimentation adds chainextender 1,4-butyleneglycol 0.61g with embodiment 16 in the preparation of aqueous polyurethane (1).
Embodiment 18:
Experimentation adds chainextender 1,4-butyleneglycol 1.35g with embodiment 16 in the preparation of aqueous polyurethane (1).
Embodiment 19:
Experimentation adds chainextender 1,4-butyleneglycol 1.8g with embodiment 16 in the preparation of aqueous polyurethane (1).
Embodiment 20:
Experimentation adds chainextender 1,4-butyleneglycol 2.25g with embodiment 16 in the preparation of aqueous polyurethane (1).
Synthetic PU/PVC emulsion resin and material property table look-up thereof among table 5 embodiment
| Embodiment number | Changing factor | Notched Izod impact strength (KJ/m 2) | Tensile strength (MPa) |
| 17 | M PU＝6000 | 24.38 | 40.60 |
| 16 | M PU＝7100 | 44.41 | 40.75 |
| 18 | M PU＝9500 | 26.20 | 40.22 |
| 19 | M PU＝14000 | 21.40 | 40.03 |
| 20 | M PU＝26000 | 21.20 | 39.60 |
Annotate: among above each embodiment, PU content all accounts for 5.66% of hybrid emulsion resins quality.
Testing data from table 5 is as can be seen: the novel polyvinyl chloride hybrid emulsion resins of the present invention's preparation, and adopt calcium zinc stabilizer to compare with organotin stabilizer, mechanical property is improved more obvious, and thermal characteristics changes little.
Embodiment 21:
In the preparation of compounded latex (3), initiator potassium persulfate changes the two 2-ethylhexyls (EHP) of peroxy dicarbonate, consumption 1.25g into; Emulsifier sodium lauryl sulfate changes the mixture of polyethylene of dispersing agent alcohol (PVA KH-20) 10g and Vltra tears (HPMC) 60g into, polyurethane-acrylate (PUA) compounded latex 89.1g, pH value conditioning agent bicarbonate of ammonia, regulation range is 7.8～8.4, polymerization temperature is 57 ± 0.5 ℃, the vinyl chloride monomer feed way is that disposable intermittence is reinforced, letex polymerization changes suspension polymerization into, the compound resin of preparation is without breakdown of emulsion, direct filtration, drying, other operating process is with embodiment 1.
Embodiment 22:
In the preparation of compounded latex (3), the polyurethane-acrylate compounded latex adds 183g, and other operation steps is with embodiment 21.
Embodiment 23:
In the preparation of compounded latex (3), the polyurethane-acrylate compounded latex adds 291g, and other operation steps is with embodiment 21.
Synthetic PUA/PVC emulsion resin and material property table look-up thereof among table 6 embodiment
| Embodiment number | Changing factor | Notched Izod impact strength (KJ/m 2) | Tensile strength (MPa) |
| 21 | 5％ | 7.68 | 47.26 |
| 22 | 10％ | 18.36 | 45.12 |
| 23 | 15％ | 35.22 | 44.39 |
Annotate: among above each embodiment, changing factor accounts for the percentage ratio of hybrid emulsion resins solid masses for the PUA compounded latex.
The present invention adopts letex polymerization and suspension polymerization, and different according to vinyl chloride monomer and seed emulsion consumption have prepared novel polychloroethylene compound resin and coating, tackiness agent, and after tested, each product high comprehensive performance has reached intended purposes.
Claims (5)
1. urethane and complex substance in-situ modified polyvinyl chloride resin thereof is characterized in that it is to prepare according to the following steps:
(1) preparation of hud typed compounded latex particle
A. Synthesis of Waterborne Polyurethane
The composition quality umber
Polyvalent alcohol 100
Isocyanic ester 20.31～31.68
Terminal hydroxy group carboxylic acid 4.48～8.96
Dibutyl tin laurate 0.000～0.002
Solvent 10～20
Thinner 10～20
Salt forming agent 3.0～6.0
Chainextender 0.0～3.0
Dispersion agent 350～400
Polyvalent alcohol refers to polyester diol (PPG), polyether Glycols and composition thereof; Solvent and thinner refer to acetone, methylethylketone, dioxane, N respectively, dinethylformamide, N-Methyl pyrrolidone or toluene; Salt forming agent refers to sodium hydroxide, ammoniacal liquor or triethylamine, and degree of neutralization is 60～100%; Chainextender refers to 1, one or more in 4-butyleneglycol, ethylene glycol, glycol ether, ethylene glycol or the TriMethylolPropane(TMP);
Above-mentioned each reactant is all carried out processed before use, polyvalent alcohol and isocyanic ester stirring reaction 1～2 hour in 60～100 ℃ of scopes, add the terminal hydroxy group carboxylic acid that has been dissolved in advance in the solvent then and continue reaction 0.5～2 hour, be cooled to 50 ℃ afterwards, add thinner and reduce viscosity, add salt forming agent again and neutralize, react after 30 minutes, add chainextender and dispersion agent high-speed stirring, dispersion and emulsion, make the self-emulsifying anion-type water-thinned polyurethane;
B. the preparation of polyurethane-acrylate composite emulsion
The composition quality umber
Self-control aqueous polyurethane 50～100
Acrylate monomer 0.0～15.3
Deionized water 32.14～45.92
Linking agent 0.0～2.6
Emulsifying agent 0.0～1.3
Initiator 0.26～1.32
Acrylate monomer refers to other acrylate of butyl acrylate (BA), 2-EHA (EHA) or second-order transition temperature Tg＜-10 ℃ and their mixture, and initiator is Potassium Persulphate (K
2S
2O
4); Emulsifying agent is selected sodium lauryl sulphate (SDS) for use; The mass ratio of urethane and polyacrylic ester is 40～100: 0～60 in the compounded latex of gained;
Under nitrogen protection, stirred 30 minutes under self-control aqueous polyurethane, deionized water and the emulsifier mix room temperature that will obtain by a step, make it fully emulsified, be warming up to 70～85 ℃ and add initiator down, dropwise addition of acrylic acid ester monomer and linking agent dropwised in 0.5～2 hour simultaneously, continued insulation reaction 1～3 hour, cooling discharge makes the polyurethane-acrylate compounded latex then;
(2) graft polymerization of vinyl chloride monomer and compounded latex
Wherein a kind of emulsion that step a or b are made joins in the autoclave, adds other component successively simultaneously, reacts under 0.4～0.9MPa;
Graft polymerization reaction adopts the mixed solution composition and the consumption of letex polymerization as follows:
The composition quality umber
Vinyl chloride monomer 100
Deionized water 200～300
Emulsifying agent 0.3～1.0
Initiator 0.3～3.0
Compounded latex 20～400
PH regulator agent 1～10
Initiator is Potassium Persulphate (K
2S
2O
4); Emulsifying agent is selected sodium lauryl sulphate (SDS) for use; The pH regulator agent is ten water Sodium Tetraboratees, sodium bicarbonate, sodium hydroxide or yellow soda ash; The mass ratio of urethane and polyacrylic ester is 40～100: 0～60 in the last step reaction gained compounded latex, and the pH regulator agent is ten water Sodium Tetraboratees, sodium bicarbonate, sodium hydroxide or yellow soda ash, and concentration is 0.5～15%, and the pH scope is 6～12;
Reaction system is airtight, vacuumize, fill nitrogen, exhaust, after the repetitive operation three times, adopt the reinforced vinyl chloride monomer that adds in continuous charging or disposable gap, after 8～16 hours, the fast cooling termination reaction is removed unreacted vinyl chloride monomer in 40～60 ℃ of following polymerizations, discharging sampling, prepared polyvinyl chloride graft polymkeric substance is freezing, breakdown of emulsion, filtration, washing, dry novel polyvinyl chloride emulsion resin.
Perhaps the emulsion polymerization of graft polymerization reaction employing is substituted by suspension polymerization,
The composition and the consumption of suspension polymerization mixed solution are as follows:
The composition quality umber
Vinyl chloride monomer 100
Deionized water 100～200
Dispersion agent 0.1～2.0/10～30
Initiator 0.2～1.0
Compounded latex 20～100
PH regulator agent 1～8
Wherein dispersion agent is polyvinyl alcohol (PVA, KH-20) and the compound system of Vltra tears (HPMC), initiator is the two 2-ethylhexyls (EHP) of peroxy dicarbonate, bicarbonate of ammonia is selected in the pH regulator agent for use, concentration is 10%, reaction system is airtight, vacuumize, fill nitrogen, after the exhaust, repetitive operation three times, adopt the reinforced vinyl chloride monomer that adds in continuous charging or disposable gap, in 40～60 ℃ of following polymerizations after 8～16 hours, the fast cooling termination reaction is removed unreacted vinyl chloride monomer, the discharging sampling, with prepared polyvinyl chloride graft polymkeric substance, filter, washing, dry novel polyvinyl chloride suspending resin.
2. according to described urethane of claim 1 and complex substance in-situ modified polyvinyl chloride resin thereof, it is characterized in that the described isocyanic ester of step a is aromatic isocyanate or aliphatic isocyanates, aromatic isocyanate is tolylene diisocyanate (TDI), ditan-4-4 '-vulcabond (MDI), liquefied mdi or poly methylene poly phenyl poly isocyanate (PAPI), aliphatic isocyanates is hexamethylene diisocyanate (HDI) or isoflurane chalcone diisocyanate (IPDI).
3. according to described urethane of claim 1 and complex substance in-situ modified polyvinyl chloride resin thereof, it is characterized in that the described terminal hydroxy group carboxylic acid of step a is self-emulsifying chainextender, dimethylol propionic acid (DMPA) or contains the carboxyl half ester.
4. according to described urethane of claim 1 and complex substance in-situ modified polyvinyl chloride resin thereof, it is characterized in that in the preparation of polyurethane-acrylate composite emulsion b, described linking agent refers to one or more the blend in allyl methacrylate(AMA), 1,4 butanediol diacrylate, allyl acrylate, Viscoat 295, diethylene glycol diacrylate, Vinylstyrene, Phthalic acid, diallyl ester, ethoxylated trimethylolpropane triacrylate, ethoxylated neopentylglycol double methacrylate and the homologue thereof.
5. according to described urethane of claim 1 and complex substance in-situ modified polyvinyl chloride resin thereof, it is characterized in that in the preparation of polyurethane-acrylate composite emulsion b, dosage of crosslinking agent is respectively 0.5～5% of amount of monomer.
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Assignee: Hebei Shenghua Chemical Industry Co., Ltd. Assignor: Hebei University of Technology Contract fulfillment period: 2008.8.23 to 2015.8.23 Contract record no.: 2008990001235 Denomination of invention: Polyurethane and its complex substance in-situ modified polyvinyl chloride resin and preparing method Granted publication date: 20080716 License type: Exclusive license Record date: 20081119 |
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