CN1070202C - Moisture penetrative and waterproof polyurethane resin and production thereof - Google Patents
Moisture penetrative and waterproof polyurethane resin and production thereof Download PDFInfo
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- CN1070202C CN1070202C CN96106937A CN96106937A CN1070202C CN 1070202 C CN1070202 C CN 1070202C CN 96106937 A CN96106937 A CN 96106937A CN 96106937 A CN96106937 A CN 96106937A CN 1070202 C CN1070202 C CN 1070202C
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- diisocyanate
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Abstract
The present invention relates to polyurethane (PU) resin with excellent water vapor permeability and water resistance and a preparation method thereof. The method comprises the following steps: using hydrophilic and hydrophobic raw materials to carry out successive polymerization reaction with diisocyanate; adjusting and preparing a hydrophilic non-porous or micro-porous PU resin according to the difference of the composition of the hydrophilic raw materials. The PU resin has water vapor permeability and water resistance, and can be applied to the manufacture of PU synthetic leather and the processing of shoes, products used in coats, etc. to cause the PU synthetic leather, shoes, products used in coats, etc. to have water vapor permeability and water resistance; the present invention greatly has an utilization value in industries.
Description
The invention relates to a kind of urethane (PU) resin and method for making thereof that has water vapour permeability and water-repellancy concurrently.
Commercially available general PU resin roughly can be divided into a liquid type dry type PU resin at present, three classes such as a binary liquid shape dry type PU resin and a liquid type wet-type PU resin, it is with organic isocyanate compound and polyalcohols reaction gained, for the organic isocyanate compound, aliphatics, aromatic series, alicyclic diisocyanate etc. and composition thereof are arranged, and polyalcohols has polyester type and polyether-type; Wherein the saturating temperature of dry type PU resin is about 500gH
2O/24hr.m
2Below, water pressure resistance is about 7000mm.H
2More than the O; Wet type resin Water Vapour Permeability is about 3000g H
2O/24hr.m
2More than, water pressure resistance is about 1000mm.H
2Below the O; If according to the requirement of general moisture-permeability waterproof, Water Vapour Permeability should reach 2000g H
2O/24hr.m
2↑, water pressure resistance should reach 3000mm.H
2O ↑ level, then aforementioned PU resin all fails to satisfy simultaneously the requirement of moisture-permeability waterproof, and is as shown in the table.Table 1 is PU resin commonly used and moisture-permeability waterproof PU resin comparison sheet of the present invention.
Table 1
| Resin properties | Wet water-fast PU resin of the present invention produces finished product | A liquid type dry type PU resin commonly used produces finished product | Binary liquid shape dry type PU resin commonly used produces finished product | A liquid type wet-type PU resin commonly used produces finished product |
| Water Vapour Permeability gH 2O/24hr.m 2 | 2000↑ | 500↓ | 500↓ | 3000↑ |
| Water pressure resistance mm.H 2O | 3000↑ | 7000↑ | 7000↑ | 1000↓ |
Main purpose of the present invention is that the PU fat manufacture method of a moisture-permeability waterproof is being provided, and by preparing two kinds of PU resins of hydrophilic and little multi-hole type, can't take into account Water Vapour Permeability and watertight shortcoming effectively to overcome aforementioned PU resin commonly used; The hydrophilic that the inventive method is made and little multi-hole type PU resin use coat weave cotton cloth or tNonwovens on the time, can produce the Water Vapour Permeability of excellence and take into account watertight performance, and then the function and the value added of lifting product.
Distinguish according to the wet thoroughly structure of resin according to the prepared moisture-permeability waterproof PU of the inventive method resin, can be divided into hydrophilic and little multi-hole type PU resin, wherein the hydrophilic resin can be divided into one-part form hydrophilic PU resin and the box-like hydrophilic PU of pre-polymerization resin again according to its reactive polymeric mode again; Now this three resinoid formula material and manufacturing process are described as follows:
One, formula material:
Hydrophilic PU resin and the spendable raw material of little multi-hole type PU resin comprise polyalcohols, isocyanic ester, chain extension agent, solvent and other auxiliary agent etc.
A. polyalcohols: divide into wetting ability and hydrophobicity; Hydrophilic have a polyoxyethylene glycol (be called for short PEG), with polyoxyethylene glycol and polypropylene glycol multipolymer (PEG/PPG COPOLYMER), hydrophobic have a polyester adipate class (polyethylene adipate, poly-hexanodioic acid ethylene propylene ester, poly-hexanodioic acid butylidene ester etc.), with poly-tetramethyl-ether ethylene glycol (being called for short PTMG) etc.; Molecular weight is between 500～4000, and the molar ratio that hydrophilic, hydrophobic property raw material uses is according to Water Vapour Permeability and watertightly require degree and adjust.The ear ratio of rubbing that hydrophilic, hydrophobic property raw material uses can be by 25: 1～1: 25, and the more then Water Vapour Permeability is better for the use of wetting ability raw material, but then more unfavorable to the water resisting property water pressure resistance, its more suitable molar ratio was advisable with 10: 1～1: 10.
B. diisocyanates: spendable have aliphatics, aromatic series, alicyclic an etc. diisocyanates, as: isophorone diisocyanate (IPDI), 1, hexamethylene-diisocyanate (TDI), 4,4 '-'-diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI) etc.
C. chain extension agent: spendable have ethylene glycol (EG), propylene glycol (PG), and 1, the 4-butyleneglycol (1,4-BG), TriMethylolPropane(TMP) (TMP) etc.
D. solvent: be organic solvent, generally use butanone (MEK), dimethyl formamide (DMF), toluene (TOL), ethyl acetate (EAc) etc.
E. auxiliary agent: (for example: phosphorous acid esters) and smooth auxiliary agent (for example silicone oil) include catalyzer (for example: tertiary amine class, organo-metallic class etc.), antioxidant.
F. emulsifying agent: be the oligomerization compound of hydrophilic, little multi-hole type PU resin uses (for example: the derivative of polyvinyl alcohol, polyvinyl alcohol, cellulosic derivative etc.).
Two, manufacturing process explanation of the present invention:
A, Fig. 1 are general PU resin manufacture flow process commonly used
See also Fig. 1, PU resin manufacture flow process commonly used is to add catalyzer with general hydrophobicity polyalcohols, auxiliary agents such as antioxidant are after 0.5～10 ton of reactive tank mixing and stirring, add di-isocyanate reaction, temperature is controlled in 50～90 ℃, carry out prepolymerization and react about 1 to 3 hour to theoretical nco value, just with the polyalcohols complete reaction, and then adding chain extension agent and solvent, stir and made it mix the molecular weight that the back was extremely designed in 50～90 ℃ of following polyreactions with vulcabond in about 4～6 hours in 10～30 minutes, add the solid shape branch of solvent and auxiliary agent adjustment at last, and make general PU resin commonly used.
The difference of maximum of the present invention is to be that the present invention introduces the wetting ability raw material in prescription and in making, as polyoxyethylene glycol (or derivatives thereof), and polyoxyethylene glycol and polypropylene glycol multipolymer etc.; Its main manufacturing process is described as follows:
B. Fig. 2 is the box-like hydrophilic moisture-permeability waterproof of a pre-polymerization PU resin manufacture flow process
See also Fig. 2, the box-like hydrophilic moisture-permeability waterproof of pre-polymerization in the inventive method PU resin manufacture flow process, this polyreaction is mainly formerly allocated the ratio 10: 1～1: 10 of hydrophilic polyalcohols and hydrophobic polyalcohols, its ratio is decided according to the institute's Water Vapour Permeability that requires and watertight specification, add catalyzer subsequently, auxiliary agents such as antioxidant in 0.5～10 ton of reactive tank with the stirring velocity of 10～100rpm and solvent stir about 10～30 minutes, after it is mixed, add di-isocyanate reaction, temperature is controlled in 50～90 ℃ and carries out prepolymerization and react about 1 to 3 hour to theoretical nco value, just with the polyalcohols complete reaction, and then adding chain extension agent, stir and made it mix the back in 10～30 minutes under 50-90 ℃, to carry out the molecular weight of about 4～6 hours of polyreaction to design with vulcabond, after adding the solid shape branch of solvent and auxiliary agent adjustment at last, divide between 20～50% and make solid shape, molecular weight is between 20,000 to 400,000.Be generally and make things convenient for the pre-polymerization mould assembly moisture-permeability waterproof PU resin of back segment processing control between 50,000 to 200,000.
C. Fig. 3 is an one-part form hydrophilic moisture-permeability waterproof PU resin manufacture flow process
See also Fig. 3, one-part form hydrophilic moisture-permeability waterproof PU resin manufacture flow process in the inventive method, main 10: 1～1: 10 of the ratio of allocating hydrophilic polyalcohols and hydrophobic polyalcohols earlier according to required wet degree and water pressure resistance degree of this polyreaction, be incorporated in 0.5～10 ton the reactive tank, then add auxiliary agents such as antioxidant, and stir with chain extension agent and solvent rotating speed in 10～100rpm, stir it was mixed in 10～30 minutes after, add di-isocyanate reaction again, temperature is controlled between 50～90 ℃, react about 4 to 8 hours to designing molecular weight, add the solid shape branch of solvent and modification agent adjustment at last, can make solid shape and divide between 20～50%, molecular weight is between 20,000 to 400,000.Be generally and make things convenient for back segment processing control between 50,000 to 200,000 one-part form hydrophilic moisture-permeability waterproof PU resin.
The box-like saturating moor reason with one-part form hydrophilic moisture-permeability waterproof PU resin of above-mentioned pre-polymerization mainly is the number that hydrophilic group exists, hydrophilic group is the more then after the resin film forming, the permeable amount of aqueous vapor just increases, the number of hydrophobic group then influences watertight degree, so adjust close and distant water base ratio, can obtain desired Water Vapour Permeability and water pressure resistance degree.
D. Fig. 4 is little multi-hole type moisture-permeability waterproof PU resin manufacture flow process
See also Fig. 4, little multi-hole type moisture-permeability waterproof PU resin manufacture flow process in the inventive method, the fore portion of this polyreaction is identical with general PU resin, promptly with hydrophobic polyalcohols and auxiliary agent, solvent adds respectively in 0.5～10 ton of reactive tank after stirring velocity stir about with 10～100rpm made it evenly in 10～30 minutes, add vulcabond, temperature is controlled in 50～90 ℃ and carries out prepolymerization and react and arrived theoretical nco value in about 1 to 3 hour, when being the polyalcohols complete reaction, add chain extension agent and solvent, mixed stir about 10-30 minute, add di-isocyanate reaction 2 to 5 hours again to designed molecular weight, then different from other adds solvent and mixed afterreaction in emulsifier for mixing 10-30 minute 1 to 3 hour with general resin, add solvent and modification agent at last, to adjust solid shape branch, can make solid shape and divide between 30～50%, molecular weight is 20,000～400,000.Be generally and make things convenient for the back segment processing tube, system is between 50,000～200, little multi-hole type moisture-permeability waterproof PU resin of 000.Because of wherein containing the composition of emulsifying agent, therefore can produce little porous form after being painted film then tempering, and reach the good special-effect that wets.
Fig. 5 is the photo of the box-like hydrophilic product of one-part form hydrophilic+pre-polymerization that makes with the inventive method (application examples 1).
Fig. 6 is the photo of pre-box-like hydrophilic+little multi-hole type product made from the inventive method (application examples 3).
For further understanding technology contents of the present invention, with following embodiment the present invention's goods applicatory are described, but are not to limit category of the present invention with this.
Embodiment 1 (according to the box-like hydrophilic PU of the prepared pre-polymerization of the inventive method resin):
In room temperature with 111 parts of toluene, 135 parts of poly-tetramethyl-ether ethylene glycol (molecular-weight average is 2000), 62.5 part polyoxyethylene glycol (molecular-weight average is 2000), after in reactor, being mixed to evenly with the anchor agitator of RPM30～60, add 23 parts of Toluene-2,4-diisocyanate .4-vulcabond again and carry out the prepolymerization reaction to theoretical nco value (0.847) in 50 ℃～90 ℃, add 0.8 part of TriMethylolPropane(TMP) and 3.75 parts of butyleneglycols one by one, and follow 110 parts of toluene with residue theoretical value 3.0 parts of Toluene-2,4-diisocyanate .4-vulcabond, 57 parts of dimethyl formamides, successive reaction to molecular weight between 50,000～100,000, Gu shape is divided into 45% PU resin (A).Its basic physical properties is: viscosity 51,000CPS/25 ℃, tension intensity 300kg/cm
2, 100%MOD.30kg/cm
2
It is as shown in the table that it makes prescription:
| The raw material name of an article | Input amount |
| Toluene gathers tetramethyl-ether ethylene glycol (MWn:2000) polyoxyethylene glycol (MWn:2000) Toluene-2,4-diisocyanate, 4-vulcabond | 221 135 62.5 26 |
| Trimethyl propane butyleneglycol dimethyl formamide | 0.8 3.75 57 |
| Add up to | 506.05 |
Embodiment 2 (according to the box-like hydrophilic PU of the prepared pre-polymerization of the inventive method resin):
In room temperature with 150 parts of butanone, 46.3 part poly-tetramethyl-ether ethylene glycol (molecular-weight average is 1000), 31.3 a part polyoxyethylene glycol (molecular-weight average is 2000) mixes earlier in reactor, add 40.6 parts of ditanes-4 again, 4 '-vulcabond carries out prepolymerization reaction to theoretical nco value (3.146%) in 50～80 ℃, add 6.23 parts of ethylene glycol, 12.5 part dimethyl formamide, 211 parts of butanone reactions obtain molecular weight between 70,000～150,000, Gu shape is divided into 25% PU resin (B);
Its basic physical properties is: viscosity 38,000 CPS/25 ℃, and tension intensity 390kg/cm
2, 100%MOD.23kg/cm
2It is as follows that it makes prescription:
| The raw material name of an article | Input amount |
| Butanols gather tetramethyl-ether ethylene glycol (MWn:1000) polyoxyethylene glycol (MWn:2000) ethylene glycol bisthioglycolate phenylmethane-4,4 '-the vulcabond dimethyl formamide | 361 46.3 31.3 6.23 40.6 12.5 |
| Add up to | 497.93 |
Embodiment 3 (according to the prepared one-part form hydrophilic of the inventive method PU resin):
In room temperature with 55 parts of poly-tetramethyl-ether ethylene glycol of 350 parts of dimethyl formamides (molecular-weight average is 2000), 45 parts of polyoxyethylene glycol (molecular-weight average is 2000), after 10.3 part butyleneglycol is mixed to evenly with the anchor agitator of RPM 30～60 in reactor, add 41.1 parts of ditanes-4 again, 4 '-vulcabond is in 60～90 ℃ of reactions, can get molecular weight between 70,000～150,000, Gu shape is divided into 30% PU resin (C).
Its basic physical properties is: viscosity 80,000 CPS/25 ℃, and tension intensity 320kg/cm
2, 100%MOD 22kg/cm
2
It is as follows that it makes prescription:
| The raw material name of an article | Input amount |
| The dimethyl methyl acid amide gather tetramethyl-ether ethylene glycol (MWn:2000) polyoxyethylene glycol (MWn:2000) butyleneglycol ditane-4,4 '-vulcabond | 350 55 45 10.3 41.1 |
| Add up to | 501.4 |
Embodiment 4 (according to the prepared multi-hole type PU of the inventive method resin):
In room temperature with 90 parts of butanone, 23 parts of ditanes-4 of 60 parts of poly-tetramethyl-ether ethylene glycol (molecular-weight average is 1000), 4 '-after vulcabond is mixed to evenly with the anchor agitator of RPM 30～60 in reactor, and carry out prepolymerization in 50～80 ℃ and react to theoretical nco value (1.554%), add 10.2 parts of ethylene glycol one by one, reacted about one hour, add 33 parts of ditanes-4 one by one, 4 '-di-isocyanate reaction, and be adjusted into solid shape with butanone and divide 30%, molecular weight is between 100,000～200,000 PU solution adds 29 parts of PU emulsifying agents and 68 parts of butanone mixing and stirring, get final product PU resin (D).Its basic physical properties is: viscosity 36,000 CPS/25 ℃, and tension intensity 146kg/cm
2, 100%MOD.31kg/cm
2Formula table is as follows:
| The raw material name of an article | Input amount |
| Butanone gather tetramethyl-ether ethylene glycol (MWn:1000) ditane-4,4 '-vulcabond ethylene glycol PU emulsifying agent (Gu shape is divided into 30%) | 295 60 56 10.2 29 |
| Add up to | 450.2 |
Can know for the moisture-permeability waterproof characteristic that makes the prepared moisture-permeability waterproof PU of the inventive method resin to represent, be illustrated with following 3 example application again.Application examples 1
Mix processing fluid,matching 1,2 with above-mentioned PU resin (A), (C) according to following prescription
| Fluid,matching 1 | Fluid,matching 2 | ||
| PU resin (C) MEK colorant viscosity | 100PHR 40～60PHR 0～20PHR 2750±250CPS/25℃ | PU resin (A) DMF MEK linking agent viscosity | 100PHR 6～12PHR 10～20PHR 4～10PHR 7000±3000CPS/25℃ |
Fluid,matching 1,2 is successively coated on 75 red Buddhist nun's polyester looped fabrics with the transfer coating method, total glue spread is 250～350g/m again
2, and, promptly get processed finished products with 70～130 ℃ of dryings 3 minutes.It is 2900g H that this finished product records Water Vapour Permeability according to the JISL-1099 method
2O/24hrm
2, recording water pressure resistance according to the JISL-1092B method again is 3200mm.H
2O; Its thoroughly wet structure is a hydrophilic, as shown in Figure 5.Application examples 2
Fluid,matching in the application examples 11,2 is successively coated on the wet process PU leather work in-process with the transfer coating method, and total glue spread is 250～350g/m
2, and, promptly getting processed finished products with 70～130 ℃ of dryings 3 minutes, it is 2180g H that this finished product records Water Vapour Permeability according to the JISL-1099 method
2O/24Hr.m
2, recording water pressure resistance according to the JISL-1092B method again is 5500mm.H
2O.Application examples 3 mixes processing fluid,matching 3,4 with above-mentioned PU resin (B), (D) according to following prescription.
| Fluid,matching 3 | Fluid,matching 4 | ||
| PU resin (B) | 100PHR | PU resin (D) | 100PHR |
| MEK colorant viscosity | 10～30PHR 0～20PHR 13,000±3,000 CPS/25℃ | MEK TOL water viscosity | 13PHR 18PHR 50～60PHR 16,000±4,000CPS/25℃ |
Fluid,matching 3,4 is successively coated on the anti-grand tTaffeta with direct coating method, total glue spread is 120～180g/m again
2, and, promptly get processed finished products with 70～160 ℃ of dryings 8 minutes.It is 3400g H that this finished product records Water Vapour Permeability according to the JISL-1099 method
2O/24hr.m
2, recording water pressure resistance according to the JISL-1092B method again is 5800mm H
2O; Its thoroughly wet structure is that hydrophilic adds little multi-hole type, as shown in Figure 6.
Claims (3)
1. the box-like hydrophilic of pre-polymerization has the urethane resin method for making of water vapour permeability and water-repellancy, comprise by selecting by polyoxyethylene glycol, the wetting ability polyalcohols that polyoxyethylene glycol and polypropylene glycol multipolymer are selected, with by polyethylene adipate, the hydrophobicity polyalcohols that poly-hexanodioic acid ethylene propylene ester and poly-hexanodioic acid butylidene ester are selected, the ratio of allotment wetting ability polyalcohols/hydrophobicity polyalcohols becomes 10: 1～and 1: 10, the catalyzer that adding is selected by tertiary amine class and organo-metallic soap class, the phosphorous acid esters antioxidant with by isophorone diisocyanate, 1, hexamethylene-diisocyanate, 4,4 '-vulcabond that '-diphenylmethane diisocyanate and tolylene diisocyanate are selected carries out the prepolymerization reaction to theoretical nco value, add again by ethylene glycol, propylene glycol, 1, the chain extension agent that 4-butyleneglycol and TriMethylolPropane(TMP) are selected, by butanone, dimethyl formamide, the solvent that toluene and ethyl acetate are selected, again with di-isocyanate reaction to designing molecular weight, and adjust solid shape and divide between 20～50%, and get molecular weight between 50,000～200,000 urethane resin forms.
2. an one-part form hydrophilic has the urethane resin method for making of water vapour permeability and water-repellancy, comprise by selecting by polyoxyethylene glycol, the wetting ability polyalcohols that polyoxyethylene glycol and polypropylene glycol multipolymer are selected, with by polyethylene adipate, the hydrophobicity polyalcohols that poly-hexanodioic acid ethylene propylene ester and poly-hexanodioic acid butylidene ester are selected, the ratio of allotment wetting ability polyalcohols/hydrophobicity polyalcohols becomes 10: 1～and 1: 10, the catalyzer that adding is selected by tertiary amine class and organo-metallic soap class, the phosphorous acid esters antioxidant, add again by ethylene glycol, propylene glycol, 1, the chain extension agent that 4-butyleneglycol and TriMethylolPropane(TMP) are selected, by butanone, dimethyl formamide, the solvent that toluene and ethyl acetate are selected, with by isophorone diisocyanate, 1, hexamethylene-diisocyanate, 4,4 '-vulcabond di-isocyanate reaction that '-diphenylmethane diisocyanate and tolylene diisocyanate are selected is to designing molecular weight, and adjust solid shape and divide between 30～50%, and get molecular weight between 50,000～200,000 urethane resin forms.
3. a little multi-hole type has the urethane resin method for making of water vapour permeability and water-repellancy, system is by selecting by polyoxyethylene glycol, the wetting ability polyalcohols that polyoxyethylene glycol and polypropylene glycol multipolymer are selected, with by polyethylene adipate, the hydrophobicity polyalcohols that poly-hexanodioic acid ethylene propylene ester and poly-hexanodioic acid butylidene ester are selected, the ratio of allotment wetting ability polyalcohols/hydrophobicity polyalcohols becomes 10: 1～and 1: 10, the catalyzer that adding is selected by tertiary amine class and organo-metallic soap class, the phosphorous acid esters antioxidant with by isophorone diisocyanate, 1, hexamethylene-diisocyanate, 4,4 '-vulcabond that '-diphenylmethane diisocyanate and tolylene diisocyanate are selected carries out the prepolymerization reaction to theoretical nco value, add again by ethylene glycol, propylene glycol, 1, the chain extension agent that 4-butyleneglycol and TriMethylolPropane(TMP) are selected, by butanone, dimethyl formamide, the solvent that toluene and ethyl acetate are selected, again with di-isocyanate reaction to designing molecular weight, add again by polyvinyl alcohol, the hydrophilic emulsifier that polyvinyl alcohol derivative and derivatived cellulose are selected, modification agent is also adjusted solid shape and is divided between 30～50%, and hydrophilic emulsifier is scattered in wherein molecular weight between 50,000～200,000 urethane resin forms.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96106937A CN1070202C (en) | 1996-07-15 | 1996-07-15 | Moisture penetrative and waterproof polyurethane resin and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96106937A CN1070202C (en) | 1996-07-15 | 1996-07-15 | Moisture penetrative and waterproof polyurethane resin and production thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1142512A CN1142512A (en) | 1997-02-12 |
| CN1070202C true CN1070202C (en) | 2001-08-29 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100519924C (en) * | 2006-05-16 | 2009-07-29 | 凯力实业股份有限公司 | Production of waterproof foaming substrate |
| CN101081895B (en) * | 2007-07-12 | 2010-08-04 | 江苏东邦化学有限公司 | Water-washing resistant moisture-permeable water-proof polyurethane resin and method for manufacturing same |
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| Publication number | Publication date |
|---|---|
| CN1142512A (en) | 1997-02-12 |
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