CN101624433B - Heat-sensitive copolymer latex, preparation method and application thereof - Google Patents
Heat-sensitive copolymer latex, preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to heat-sensitive copolymer latex, a preparation method and an application thereof. The polymeric monomer is in mass percentage as follows: 40 percent to 75 percent of aliphatic conjugate diolefin monomer of C4 to C5, 20 percent to 50 percent of vinyl unsaturated monomer and 1.5 percent to 10 percent of unsaturated carboxylic acid or unsaturated amide monomer or mixture thereof. The preparation method comprises a prereaction stage, a continuous polymerzation stage and a post treatment stage as well as the application in the field of non-woven dipped articles or paperboard dipped articles. The invention has the advantages that: two-stage polymeric technique which has simple technique, stable reaction process, short reaction time and high polymerization conversion rate is adopted; the polymerization formula does not adopt a non-ionic emulsifying agent, and improves the heat-sensitive property of products, the heat-sensitive freezing point of the latex is lower; the glass transition temperature of the glass heat-sensitive copolymer is moderate, and the dipped product has good hand feeling and is compact, and has excellent resilience, size stability and higher strength; and the heat-sensitive complex of the latex has excellent storing stability.
Description
[technical field]
The present invention relates to carboxyl copolymer latex technology field, specifically, is a kind of heat-sensitive copolymer latex.
[background technology]
Handling immersion non-woven fabrics that non-woven fabrics, fibre product (cardboard) make, varnished pressboard etc. with latex or latex compound proofing is the main raw material of imitation leather leatheroid, leather goods, leather shoes, lining, industrial gloves, leather trunk suitcase liner, artificial leather base fabric and the footwear that are widely used as footwear, cap with in the end, packet header etc.Wherein, the effect of tackiness agent is to improve the form and the dimensional stability of product, improves the characteristic of brute force, stiffness and some others of increase of product.The performance of tackiness agent has determined the inner quality of the finished product to a great extent, and wherein the thermo-sensitivity of latex is the most important factor that influences product performance.
In order to improve the infusion product quality, often adopt the temperature-sensitive impregnation technology.The temperature-sensitive impregnation technology generally adopts NBR; Heat-sensitive glues such as SBR to improve the compactness of grey cloth, improve its crooked recoverability; Pass through the chemical adhesion effect of latex in addition; The S-S characteristic of grey cloth is improved, and after washing, form the microvoid structure of similar animal cortex, to increase the water absorbability and the ventilation property of base cloth.Making like the imitation leather artificial leather base fabric is exactly the method that adopts the temperature-sensitive dipping, with non-woven fabrics through proofing drill traverse glue, heat drying, the latex temperature-sensitive is condensed in fiber,, polishing dry through washing, the extruding artificial leather base fabric that gets product.Generally with the soaker of synthetic latex as non-woven fabrics, fibre product (cardboard), used latex comprises paracril latex (NBR1), styrene butadiene rubber latex (SBRL) etc., to improve the compactness of grey cloth, improves its crooked recoverability, and feel.U.S. Pat 5629047 provides a kind of preparation method who is used for the latex of non-woven fabrics proofing, comprises that the monomer such as vi-ny l aromatic monomers and a spot of vinylformic acid, methylacrylic acid, methylene-succinic acid of the conjugate diene monomer that uses 35～60 weight % and 30～65 weight % carries out low temperature (5 ℃) emulsion polymerization in the presence of emulsifying agent.German Patent Ger1243394 provides a kind of thermo-sensitivity rubber latex; Through adopting negatively charged ion and nonionic composite emulsifying system, the monomer mixture that letex polymerization is made up of the vinyl cyanide of the divinylic monomer of 50～85 weight %, 14～49 weight % or vi-ny l aromatic monomers vinylbenzene, the methylacrylic acid of 1～8 weight % in the presence of initiator obtains; 20 ℃ of polymerization temperatures, transformation efficiency 90%; Has desired zero pour after the effect of product temperature-sensitive.The Chinese patent publication number CN1640899 provide a kind of heat-sensitive copolymer latex, its preparation method and application; Its characteristics add the non-ionic polyalcohol of 0.01～5 weight % and the Nano-class zinc oxide of 0～5 weight % in the unsaturated carboxylic acid monomer mixture of the acrylate monomer of the aliphatic conjugated diene monomer that contains 20～70 weight %, 20～70 weight % and 0～10 weight %, carry out letex polymerization then; The heat-sensitive copolymer latex of invention can be used for non-woven fabrics dipping preparation imitation leather artificial leather base fabric.
In above-mentioned patent, U.S. Pat 5629047 is used low temperature (5 ℃) letex polymerization route, long reaction time; Transformation efficiency is not high, need to reclaim unreacted monomer, and the conjugate diene monomer ratio is lower in the polymerization formula; The multipolymer second-order transition temperature is higher, and the infusion product feel is not good enough; German Patent Ger1243394 has used negatively charged ion and nonionic composite emulsifying system, the emulsifying agent large usage quantity, and the latex thermo-sensitive property is relatively poor, and polymerization temperature is lower, and transformation efficiency lower (being 90%) needs to reclaim operations such as unreacted monomer, and production efficiency is not high; Chinese patent publication number CN1640899 directly adds non-ionic polyalcohol and the zinc oxide linking agent with thermo-sensitivity when synthetic latex, make polyreaction unstable, and in latex stores, is prone to condensation prod.
Based on above-mentioned technology status; The present invention develops a kind of improved heat-sensitive copolymer latex, to overcome that above-mentioned patent long reaction time, polyreaction are unstable, the infusion product feel is not good enough, the latex thermo-sensitive property is relatively poor and latex is prone to the defective of condensation prod in storing.
[summary of the invention]
The objective of the invention is to overcome the deficiency of prior art, a kind of heat-sensitive copolymer latex is provided.
The objective of the invention is to realize through following technical scheme:
A kind of heat-sensitive copolymer latex, its polymerization single polymerization monomer mass percent is:
The aliphatics conjugated diene monomer 40～75% of C4～C5
Unsaturated vinyl monomer 20～50%
Unsaturated carboxylic acid or unsaturated acyl amine monomers or its mixture 1.5～10.0%
The aliphatics conjugated diene monomer of described C4～C5 is selected from 1,3-butadiene, isoprene, one or several mixtures in the 1,3-pentadiene;
The preferred 1,3-butadiene of aliphatics conjugated diene monomer of described C4～C5;
Described unsaturated vinyl monomer is selected from TEB 3K, vinylbenzene, one or several mixtures in the vinyl cyanide;
Described unsaturated vinyl monomer optimization styrene, a kind of or two kinds of mixtures in the vinyl cyanide;
Described unsaturated carboxylic acid is selected from vinylformic acid, methylacrylic acid, methylene-succinic acid, toxilic acid, one or several mixtures in the fumaric acid;
Described unsaturated carboxylic acid is preferably methylacrylic acid or 2: 1～4: 1 methylacrylic acid of mass ratio and acrylic acid mixture;
The second-order transition temperature of heat-sensitive copolymer latex is-45 ℃ to 0 ℃, and minimum film-forming temperature is-45 ℃ to-5 ℃;
Another object of the present invention provides a kind of preparation method of heat-sensitive copolymer latex, and concrete steps are:
(1) the pre-reaction stage
With unsaturated carboxylic acid, emulsifying agent, ionogen, reductive agent and sequestrant are mixed with aqueous phase solution with deionized water dissolving, are added in the reaction kettle; Again with the aliphatics conjugated diene monomer, unsaturated vinyl monomer, molecular weight regulator is added in the reaction kettle separately or after in encloses container, mixing; High-speed stirring 15～45min is warming up to 30～60 ℃, adds pre-configured initiator solution after preferred 35～50 ℃, begins reaction;
Described emulsifying agent is an anionic emulsifier, like the sodium alkyl sulfate of C8～C20, and the sodium alkyl benzene sulfonate of C8～C20, the alkaryl polyethers sodium sulfate of C8～C20 and their mixture, its consumption are 2～5wt% of monomer weight; Preferred emulsifier is a sodium lauryl sulphate, and sodium lauryl sulphate is 3.0～4.0wt% of monomer weight;
Described ionogen is a Repone K, sodium-chlor or yellow soda ash etc.;
Described sequestrant is YD 30 and disodium salt thereof, writes a Chinese character in simplified form EDTA;
Described reductive agent is rongalite or sodium sulfite anhy 96;
Described molecular weight regulator is uncle-DDM dodecyl mercaptan, just-and DDM dodecyl mercaptan or their mixture;
Described initiator is thermal initiator or redox initiator; Thermal initiator such as persulphate, redox initiator such as persulphate and sodium sulfite anhy 96, persulphate and mercaptan, persulphate and rongalite (rongalite); Preferred initiator is persulphate and rongalite, and persulphate and rongalite mass ratio are 1: 0.5～1: 1.0, and persulphate is 0.3～0.6% of a total monomer weight; Initiator is joined deionized water be made into initiator solution;
(2) the successive polymerization stage
With unsaturated carboxylic acid, emulsifying agent is subsequent use with the deionized water wiring solution-forming; Initiator is joined deionized water be made into initiator solution; With the aliphatics conjugated diene monomer, unsaturated vinyl monomer, molecular weight regulator are mixed into the monomer oil-phase solution in encloses container subsequent use;
Sampling analysis transformation efficiency after reaction is carried out 80～90 minutes after first materials conversion rate reaches 60%, adds the residue unsaturated carboxylic acid, emulsifier aqueous solution continuously; Initiator solution, and monomer oil-phase solution, control adding speed; Make the monomer oil-phase solution, unsaturated carboxylic acid and emulsifier solution, initiator solution added in 2.5～3 hours; Be incubated 2～3h again, the postcooling discharging is accomplished in reaction, obtains latex;
(3) post-processing stages
The latex of gained slowly adds the alkali neutralization, filters, and obtains the latex finished product, i.e. heat-sensitive copolymer latex;
In letex polymerization of the present invention, carry out in order to make stable polymerization reaction, monomer adopts and adds mode in batches, adds monomer first and accounts for 20～50% of total monomer weight; The unsaturated carboxylic acid mode that adds can be disposable adding also to add in batches, add the fashionable unsaturated carboxylic acid monomer that adds first in batches and account for more than 80% of total unsaturated carboxylic acid monomer weight; Emulsifying agent adopts twice adding mode or semicontinuous adding mode, and adding consumption first is more than 85% of emulsifying agent total amount;
In letex polymerization of the present invention, as required, ionogen can also in polymerization reaction system, be added, sequestrant, buffer reagent, various auxiliary agents such as dispersion agent; These materials use with convention amount usually;
In letex polymerization of the present invention, in reactor drum, add the water of specified amount earlier, above-mentioned unsaturated carboxylic acid; Emulsifying agent and various compounding agent solution; Monomer and molecular weight regulator add initiator solution, rest part monomer when being warming up to temperature of reaction; Emulsifying agent and various compounding agent solution, and unsaturated carboxylic acid, molecular weight regulator etc. add in polymerization process continuously; When polymerisation conversion termination reaction greater than 99% time, final latex solid content 40 ± 1%;
A purpose more of the present invention provides heat-sensitive copolymer latex in non-woven fabrics dipped goods or cardboard dipped goods Application for Field; When dipping, need latex and thermosensitizing agent; The mixing of sulfuration slurry is made into title complex and uses; The weight percent of various components is: latex is 80～98%, and thermosensitizing agent is 1～10%, and the sulfuration slurry is 1～10%; General latex heat sensitizer commonly used has inorganic and organic ammonium salt, inorganic and organic zinc ammonia complex, and the polyvinyl methyl ether, W 166, trypsinase, silicon are heat sensitizing agent etc.; The sulfuration slurry is thiofide, the dispersion-s of zinc oxide etc.; Heat-sensitive copolymer latex of the present invention has excellent thermo-sensitive property, and title complex temperature-sensitive zero pour is generally between 42～48 ℃.
Compared with prior art, positively effect of the present invention is:
Two sections polymerization techniques are adopted in heat-sensitive copolymer latex preparation of the present invention, and this technology is simple, and reaction process is steady, and the reaction times is short, and polymerisation conversion is high; Reaction process does not need cryogenic coolant and complicated MONOMER RECOVERY and degasification technique; Do not adopt nonionic emulsifying agent in the polymerization formula, improved the thermo-sensitive property of product, latex temperature-sensitive zero pour is lower; This heat-sensitive copolymer second-order transition temperature is moderate, the infusion product good hand touch, and densification, rebound resilience and excellent size stability, intensity is higher; The latex heat-sensitive complex has excellent storage stability, and coagulum does not appear in 48h in storage below-40 ℃.
[embodiment]
Below provide a kind of heat-sensitive copolymer latex of the present invention and its production and application embodiment.
Total monomer add-on in embodiment and comparative example is in 100wt% (weight percentage).
Emulsion polymerization is equipped with whisking appliance using nitrogen replacement, carries out in 10 liters of stainless steel autoclaves of adjustable temperature.
Latex thermo-sensitivity test recipe of the present invention is as shown in table 1.
Table 1 latex thermo-sensitivity test recipe
| Form | Proportioning (butt) |
| Latex | 100 |
| Sulphur | 1.50 |
| Zinc oxide | 1.50 |
| Vulcanization accelerator EZ | 0.6 |
| Vulcanizating accelerant MZ | 0.5 |
| The polyvinyl methyl ether | 0.25 |
| Antioxidant 1010 | 1.00 |
| Ammonium chloride | 0.90 |
Embodiment 1
In reactor drum, add entry 135wt%, sodium lauryl sulphate 2.75wt%, methylacrylic acid 3.0wt%; Vinylbenzene 15wt%, uncle-DDM dodecyl mercaptan 0.4wt%, EDTA 0.4wt%, rongalite 0.32wt%; Divinyl 17wt% stirs and is warming up to 50 ℃, adds initiator potassium persulfate 0.40wt%, carries out polymerization about 1.5 hours; In 2.75～3 hours, add entry 15%, sodium lauryl sulphate 0.25wt%, vinylbenzene 30wt% afterwards continuously; The mixture of divinyl 35wt%, polymerization 6.5～7.5 hours, termination reaction.
Using in the ammoniacal liquor with emulsion is 7.0 to pH, final latex solid content 39.7%.
Through the thermo-sensitivity test, 48 ℃ of temperature-sensitive title complex thermally sensitive temperatures, the temperature-sensitive coagulum is tight, and intensity is high.Dipping artificial leather base fabric performance is as shown in table 2.
The varnished pressboard feel is moderate, and intensity is high, and performance reaches request for utilization.The varnished pressboard performance is as shown in table 3.
Embodiment 2
In reactor drum, add entry 135wt%, sodium lauryl sulphate 3.5wt%, methylacrylic acid 3.5wt%; Vinyl cyanide 15wt%, uncle-DDM dodecyl mercaptan 0.3wt%, EDTA 0.2wt%, divinyl 15wt%; Stirring also is warming up to 50 ℃, adds initiator potassium persulfate 0.60wt%, carries out polymerization about 1.5 hours; In 2.75～3 hours, add entry 15%, sodium lauryl sulphate 0.50wt%, vinyl cyanide 31wt% afterwards continuously; The mixture of divinyl 35.5wt%, polymerization 6.5～7.5 hours, termination reaction.
Using in the ammoniacal liquor with emulsion is 7.0 to pH, final latex solid content 39.4%.
Through the thermo-sensitivity test, 45 ℃ of temperature-sensitive title complex thermally sensitive temperatures, the temperature-sensitive coagulum is tight, and intensity is high.Dipping base cloth feel is moderate.Dipping artificial leather base fabric performance is as shown in table 2.The varnished pressboard performance is as shown in table 3.
Embodiment 3
In reactor drum, add entry 135wt%, sodium lauryl sulphate 3.25wt%, methylacrylic acid 2.0wt%; Vinylformic acid 1.0wt%, vinylbenzene 15wt%, uncle-DDM dodecyl mercaptan 0.32wt%, Repone K 0.02wt%; Rongalite 0.30wt%, EDTA 0.05wt%, divinyl 15wt% stirs and is warming up to 50 ℃; Add initiator potassium persulfate 0.30wt%, carried out polymerization about 1.5 hours, in 2.5～2.75 hours, add entry 15%, sodium lauryl sulphate 0.25wt% afterwards continuously; Vinylbenzene 32wt%, the mixture of divinyl 35wt%, polymerization 6.5～7.5 hours, termination reaction.
Using in the ammoniacal liquor with emulsion is 7.0 to pH, final latex solid content 39.7%.
Through the thermo-sensitivity test, 47 ℃ of temperature-sensitive title complex thermally sensitive temperatures, the temperature-sensitive coagulum is tight, and intensity is high; Dipping base cloth feel is moderate.Dipping artificial leather base fabric performance is as shown in table 2, and the varnished pressboard performance is as shown in table 3.
Embodiment 4
In reactor drum, add entry 135wt%, sodium lauryl sulphate 3.25wt%, methylacrylic acid 3.0wt%; Vinylbenzene 15wt%, uncle-DDM dodecyl mercaptan 0.32wt%, Repone K 0.02wt%, rongalite 0.30wt%; EDTA 0.05wt%, divinyl 15wt% stirs and is warming up to 50 ℃, adds initiator potassium persulfate 0.30wt%; Carry out polymerization about 1.5 hours, and in 2.5～2.75 hours, added entry 15%, sodium lauryl sulphate 0.25wt%, vinylbenzene 12wt% afterwards continuously; Vinyl cyanide 20wt%, the mixture of divinyl 35wt%, polymerization 6.5～7.5 hours, termination reaction.
Using in the ammoniacal liquor with emulsion is 7.0 to pH, final latex solid content 39.2%.
Through the thermo-sensitivity test, 46 ℃ of temperature-sensitive title complex thermally sensitive temperatures, the temperature-sensitive coagulum is tight, and intensity is high; Dipping base cloth feel is moderate.Dipping artificial leather base fabric performance is as shown in table 2, and the varnished pressboard performance is as shown in table 3.
Embodiment 5
In reactor drum, add entry 130wt%, sodium lauryl sulphate 3.5wt%, methylacrylic acid 2.50wt%, vinylbenzene 15wt%; Uncle-DDM dodecyl mercaptan 0.32wt%, Repone K 0.02wt%, rongalite 0.30wt%, EDTA 0.03wt%, divinyl 15wt%; Stirring also is warming up to 50 ℃, adds initiator potassium persulfate 0.30wt%, carries out polymerization 1.5 hours, in 2.75～3 hours, adds entry 20% afterwards continuously; Methylacrylic acid 0.50wt%, Potassium Persulphate 0.15wt%, sodium lauryl sulphate 0.50wt%, vinylbenzene 12wt%; Vinyl cyanide 20wt%, the mixture of divinyl 35wt%, polymerization 6.5～7.5 hours, termination reaction.
Using in the ammoniacal liquor with emulsion is 7.0 to pH, final latex solid content 39.5%.
Through the thermo-sensitivity test, 48 ℃ of temperature-sensitive title complex thermally sensitive temperatures, the temperature-sensitive coagulum is tight, and intensity is high; Dipping base cloth feel is moderate.Dipping artificial leather base fabric performance is as shown in table 2, and the varnished pressboard performance is as shown in table 3.
Embodiment 6
In reactor drum, add entry 130wt%, sodium lauryl sulphate 3.5wt%, methylacrylic acid 3.50wt%, vinylformic acid 0.50wt%; Vinylbenzene 12wt%, uncle-DDM dodecyl mercaptan 0.30wt%, Repone K 0.02wt%, rongalite 0.30wt%; EDTA 0.02wt%, divinyl 17wt% stirs and is warming up to 45 ℃, adds initiator potassium persulfate 0.35wt%; Carry out polymerization 2 hours, and in 2.75～3 hours, added entry 20%, Potassium Persulphate 0.20wt%, sodium lauryl sulphate 0.20wt% afterwards continuously; Vinylbenzene 24wt%, the mixture of divinyl 43wt%, polymerization 6.5～7.0 hours, termination reaction.
Using in the ammoniacal liquor with emulsion is 7.0 to pH, final latex solid content 39.3%.
Through the thermo-sensitivity test, 46 ℃ of temperature-sensitive title complex thermally sensitive temperatures, the temperature-sensitive coagulum is tight, and intensity is high; The dipping base cloth is soft.Dipping artificial leather base fabric performance is as shown in table 2.
Embodiment 7
In reactor drum, add entry 130wt%, sodium lauryl sulphate 3.65wt%, methylacrylic acid 3.50wt%, vinylbenzene 6wt%; Uncle-DDM dodecyl mercaptan 0.30wt%, Repone K 0.02wt%, rongalite 0.30wt%, EDTA 0.02wt%; Divinyl 20wt% stirs and is warming up to 45 ℃, adds initiator potassium persulfate 0.35wt%, carries out polymerization 2 hours; In 2.75～3 hours, add entry 20%, Potassium Persulphate 0.20wt%, sodium lauryl sulphate 0.15wt%, methylacrylic acid 0.50wt% afterwards continuously; Vinylbenzene 15wt%, the mixture of divinyl 55wt%, polymerase 17 .0～7.5 hour, termination reaction.
Using in the ammoniacal liquor with emulsion is 7.0 to pH, final latex solid content 39.6%.
Through the thermo-sensitivity test, 42 ℃ of temperature-sensitive title complex thermally sensitive temperatures, the temperature-sensitive coagulum is tight, and intensity is high; The dipping base cloth is soft.Dipping artificial leather base fabric performance is as shown in table 2.
Comparative example 1
In reactor drum, add entry 130wt%, sodium lauryl sulphate 3.5wt%, polyoxyethylene octylphenol ether (OP-10) 2.0wt%, vinylformic acid 4.0wt%; Vinylbenzene 6wt%, uncle-DDM dodecyl mercaptan 0.30wt%, Repone K 0.02wt%, rongalite 0.30wt%; EDTA 0.02wt%, divinyl 20wt% stirs and is warming up to 50 ℃, adds initiator potassium persulfate 0.35wt%; Carry out polymerization 2 hours, and in 3 hours, added entry 20%, Potassium Persulphate 0.20wt%, sodium lauryl sulphate 0.25wt% afterwards continuously; Vinylbenzene 15wt%, the mixture of divinyl 55wt%, polymerase 17 .0～7.5 hour, termination reaction.
Using in the ammoniacal liquor with emulsion is 7.0 to pH, final latex solid content 39.4%.
Through the thermo-sensitivity test, 56 ℃ of temperature-sensitive title complex thermally sensitive temperatures, the temperature-sensitive coagulum is loose, and intensity is low; The dipping base cloth is soft.Dipping artificial leather base fabric performance is as shown in table 2, and the varnished pressboard performance is as shown in table 3.
Comparative example 2
In reactor drum, add entry 130wt%, sodium lauryl sulphate 4.5wt%, polyoxyethylene octylphenol ether (OP-10) 1.0wt%, methylacrylic acid 1.0wt%; Vinylformic acid 2.5wt%, vinylbenzene 6.5wt%, uncle-DDM dodecyl mercaptan 0.30wt%, Repone K 0.02wt%, rongalite 0.30wt%; EDTA 0.02wt%, divinyl 20wt% stirs and is warming up to 50 ℃, adds initiator potassium persulfate 0.45wt%; Carry out polymerization 2 hours, and in 3 hours, added entry 20%, Potassium Persulphate 0.25wt%, sodium lauryl sulphate 0.25wt% afterwards continuously; Vinylbenzene 15wt%, the mixture of divinyl 55wt%, polymerase 17 .0～7.5 hour, termination reaction.
Using in the ammoniacal liquor with emulsion is 7.0 to pH, final latex solid content 39.6%.
Through the thermo-sensitivity test, 60 ℃ of temperature-sensitive title complex thermally sensitive temperatures, temperature-sensitive coagulum are pasty state, no intensity; The dipping base cloth is soft.Dipping artificial leather base fabric performance is as shown in table 2; The varnished pressboard performance is as shown in table 3.
Comparative example 3
In reactor drum, add entry 135wt%, sodium lauryl sulphate 3.0wt%, methylacrylic acid 3.0wt%, vinylbenzene 20wt%; Uncle-DDM dodecyl mercaptan 0.4wt%, EDTA 0.2wt%, divinyl 15wt% stirs and is warming up to 50 ℃; Add initiator potassium persulfate 0.40wt%, carried out polymerization 1.5 hours, in 3 hours, add entry 15%, sodium lauryl sulphate 0.50wt% afterwards continuously; Vinylbenzene 32wt%, the mixture of divinyl 30.0wt%, polymerase 17 .0～7.5 hour, termination reaction.
Using in the ammoniacal liquor with emulsion is 7.0 to pH, final latex solid content 39.4%.
Through the thermo-sensitivity test, 58 ℃ of temperature-sensitive title complex thermally sensitive temperatures, the temperature-sensitive coagulum is tight, and intensity is high, but nonelastic; Dipping base cloth feel is too hard.Dipping artificial leather base fabric performance is as shown in table 2; Varnished pressboard is harder, and performance is as shown in table 3.
Table 2 dipping artificial leather base fabric performance
Table 3 varnished pressboard performance
| Embodiment | Red shortness (%) (150 ℃ of * 5min) | Tensile strength (N/5cm) | Bent rich number of times (inferior) |
| Embodiment 1 | 2.0 | 127 | 1564 |
| Embodiment 2 | 1.8 | 119 | 1598 |
| Embodiment 3 | 1.7 | 117 | 1574 |
| Embodiment 4 | 1.8 | 125 | 1485 |
| Embodiment 5 | 1.3 | 124 | 1463 |
| Comparative example 1 | 2.5 | 92 | 1404 |
| Comparative example 2 | 2.8 | 94 | 1380 |
| Comparative example 3 | 1.8 | 112 | 863 |
The above only is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the present invention's design; Can also make some improvement and retouching, these improvement and retouching also should be regarded as in protection scope of the present invention.
Claims (2)
1. the preparation method of a heat-sensitive copolymer latex is characterized in that,
The polymerization single polymerization monomer mass percent is:
The aliphatics conjugated diene monomer 40～75% of C4～C5
Unsaturated vinyl monomer 20～50%
Unsaturated carboxylic acid or unsaturated acyl amine monomers or its mixture 1.5～10.0%
The aliphatics conjugated diene monomer of described C4～C5 is selected from 1,3-butadiene, isoprene, one or several mixtures in the 1,3-pentadiene;
Described unsaturated vinyl monomer is selected from TEB 3K, vinylbenzene, one or several mixtures in the vinyl cyanide;
Described unsaturated carboxylic acid is selected from vinylformic acid, methylacrylic acid, methylene-succinic acid, toxilic acid, one or several mixtures in the fumaric acid;
Concrete steps are:
(1) the pre-reaction stage
With unsaturated carboxylic acid, emulsifying agent, ionogen, reductive agent and sequestrant are mixed with aqueous phase solution with deionized water dissolving, are added in the reaction kettle; Again with the aliphatics conjugated diene monomer, unsaturated vinyl monomer, molecular weight regulator is added in the reaction kettle separately or after in encloses container, mixing; High-speed stirring 15～45min is warming up to the pre-configured initiator solution of adding after 30～60 ℃, begins reaction;
Wherein,
Described emulsifying agent is a sodium lauryl sulphate, and sodium lauryl sulphate is 3.0～4.0% of a monomer weight;
Described initiator is persulphate and rongalite, and persulphate and rongalite mass ratio are 1: 0.5～1: 1.0, and persulphate is 0.3～0.6% of a total monomer weight;
(2) the successive polymerization stage
With unsaturated carboxylic acid, emulsifying agent is subsequent use with the deionized water wiring solution-forming; Initiator is joined deionized water be made into initiator solution; With the aliphatics conjugated diene monomer, unsaturated vinyl monomer, molecular weight regulator are mixed into the monomer oil-phase solution in encloses container subsequent use;
Sampling analysis transformation efficiency after reaction is carried out 80～90 minutes after first materials conversion rate reaches 60%, adds the residue unsaturated carboxylic acid, emulsifier aqueous solution continuously; Initiator solution, and monomer oil-phase solution, control adding speed; Make the monomer oil-phase solution, unsaturated carboxylic acid and emulsifier solution, initiator solution added in 2.5～3 hours; Be incubated 2～3h again, the postcooling discharging is accomplished in reaction, obtains latex;
Monomer adopts and adds mode in batches, adds monomer first and accounts for 20～50% of total monomer weight; It can be that disposable adding also can add in batches that unsaturated carboxylic acid adds mode, adds the fashionable unsaturated carboxylic acid monomer that adds first in batches and accounts for more than 80% of total unsaturated carboxylic acid monomer weight; Emulsifying agent adopts twice adding mode or semicontinuous adding mode, and adding consumption first is more than 85% of emulsifying agent total amount;
(3) post-processing stages
The latex of gained slowly adds the alkali neutralization, filters, and obtains the latex finished product, is heat-sensitive copolymer latex.
2. the heat-sensitive copolymer latex that obtains of the method for claim 1 is in non-woven fabrics dipped goods or cardboard dipped goods Application for Field; It is characterized in that; When dipping, need latex and thermosensitizing agent, the mixing of sulfuration slurry is made into title complex and uses, and the weight percent of component is: latex is 80～98%; Thermosensitizing agent is 1～10%, and the sulfuration slurry is 1～10%.
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| CN101885808B (en) * | 2010-07-27 | 2012-03-21 | 湘潭百利新材料研究有限公司 | Emulsion polymer adhesive used for waterproof, oil-proof and antifriction thermal sensitive paper |
| CN102887977B (en) * | 2011-07-22 | 2014-05-21 | 山东九龙石化有限公司 | Production method of styrene modified carboxylic butadiene-acrylonitrite latex |
| CN103535927B (en) * | 2013-11-04 | 2015-09-09 | 山东星宇手套有限公司 | A kind of latex temperature-dependent mechanical embossing gloves and preparation technology thereof |
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