CN108864400A - A kind of high-performance cationic water polyurethane resin and preparation method thereof - Google Patents
A kind of high-performance cationic water polyurethane resin and preparation method thereof Download PDFInfo
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- C08G18/30—Low-molecular-weight compounds
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- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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Abstract
The present invention provides a kind of high-performance cationic water polyurethane resin and preparation method thereof, and resin includes following raw material components：Polyalcohol, polyisocyanates, the first small molecule chain extender, cationic hydrophilic chain extender, silane coupling agent, salt forming agent, the second small molecule chain extender；There is cyclic structure on polyol molecule chain of the present invention, improve mechanical strength, wearability and the solvent resistance of aqueous polyurethane glue film.A small amount of castor oil polyhydric alcohol is added, improves water resistance, the degree of cross linking, mechanical strength, molecular weight, the water resistance of polyurethane.Silane coupling agent γ-glycidyl ether oxygen propyl trimethoxy silicane is added in resin synthesis process, improve the mechanical strength and molecular weight of film, waterborne polyurethane resin of the invention not only has high solids content, high intensity, high molecular weight, also there is excellent adhesive force, water resistance, solvent resistance.
Description
Technical field
The present invention relates to high molecular polymer field, more particularly to a kind of high-performance cation aqueous polyurethane resin and
Preparation method.
Background technique
Aqueous polyurethane is using water as decentralized medium, compared with solvent borne polyurethane, have it is non-ignitable, smell is small, energy conservation, operation
The advantages that facilitating has been widely used as leather finishing agent, coating and adhesive etc..
With the development of aqueous polyurethane synthetic technology, performance is being continuously improved, in recent years, the application of aqueous polyurethane
Field is constantly expanded.Currently, it is in fields such as coating, adhesive, leather finishing agents using more and more extensive.But with solvent type
Polyurethane is compared, and standard aqueous polyurethane exists at present contains low, glue film water resistance, poor solvent resistance admittedly, and low wait of glue film intensity lacks
It falls into, this will produce bigger effect the application of aqueous polyurethane.Therefore, the performance deficiency for overcoming aqueous polyurethane, develops height
Performance aqueous polyurethane has great importance.
Summary of the invention
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide a kind of high-performance is cation-type water-thinned
Polyurethane resin and preparation method thereof, the modified aqueous polyurethane resin not only have high solids content, high intensity, high molecular weight,
Also there is excellent adhesive force, water resistance, solvent resistance.
In order to achieve the above objects and other related objects, the present invention provides a kind of high-performance cation-type water-thinned polyurethane tree
Rouge and preparation method thereof, the resin include following raw material components and parts by weight：
Preferably, the polyalcohol is 45~60 parts.
Preferably, the polyisocyanates is 30~38 parts.
Preferably, first small molecule chain extender is 4~5 parts.
Preferably, the cationic hydrophilic chain extender is 2~3 parts.
Preferably, the silane coupling agent is 1~2 part.
Preferably, the salt forming agent is 2~3 parts.
Preferably, second small molecule chain extender is 3~4 parts.
Preferably, the polyalcohol be UM-90, three kinds of mixing in the pure and mild castor oil of aliphatic polyester binary.
Preferably, the weight ratio of the pure and mild castor oil of the UM-90, the aliphatic polyester binary is (4~5)：
(35~45)：(6~10).
Preferably, the aliphatic polyester binary alcohol is selected from one of polycarbonate glycol and polycaprolactone diols
Or two kinds.
Preferably, the structural formula of the UM-90 is as follows：
Wherein, the integer that n is 1~1000.
Preferably, the UM-90 number-average molecular weight is 900.
Preferably, the number-average molecular weight of the castor oil is 1000,2000,3000.
It is highly preferred that the number-average molecular weight of the castor oil is 2000.
Preferably, the number-average molecular weight of the polycarbonate glycol is 1000,2000.
It is highly preferred that the number-average molecular weight of the polycarbonate glycol is 1000.
Preferably, the number-average molecular weight of the polycaprolactone diols is 1000,2000.
It is highly preferred that the number-average molecular weight of the polycaprolactone diols is 2000.
Preferably, the diisocyanate is selected from toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, isophorone
Any one in diisocyanate, hexamethylene diisocyanate and dicyclohexyl diisocyanate is a variety of.
Preferably, first small molecule chain extender is ethylene glycol, 1,4-butanediol, 2- methyl-1,3-propanediol, Isosorbide-5-Nitrae-
Any one or more in cyclohexanedimethanol.
Preferably, second small molecule chain extender is in ethylenediamine, Isosorbide-5-Nitrae-hexamethylene dimethylamine, isophorone diamine
It is one or more.
Preferably, the cationic hydrophilic chain extender is diethanol amine or N methyldiethanol amine.
Preferably, the salt forming agent is lactic acid.
Preferably, silane coupling agent includes γ-glycidyl ether oxygen propyl trimethoxy silicane, and structural formula is：
The invention also discloses a kind of method for preparing aforementioned high-performance cationic water polyurethane resin, the methods
Include the following steps：
1) it is added 40~65 parts of polyalcohol into three-necked flask, 3~5 parts of the first small molecule chain extender and 25~40 parts
Polyisocyanates, be stirred, mixing speed is 200~500r/min, is heated to 80~90 DEG C, keeps the temperature 3~5h, obtains
To the first performed polymer；
2) after the first performed polymer prepared by step 1) being cooled to 40~50 DEG C, 2~4 parts of cationic hydrophilic is added
Chain extender keeps the temperature 1~2h, obtains the second performed polymer；
3) 30~40 DEG C are cooled to, 0.5~2 part of silane coupling agent, heat preservation 5 are added into the second prepared performed polymer
~20min, then add 20~40 parts of acetone solvent, 2~4 parts of salt forming agent, 100~120 parts of tap water and 2~
4 parts of the second small molecule chain extender, continues after being stirred to react 0.5~1h, vacuum distillation, and it is cation-type water-thinned poly- to obtain high-performance
Urethane resin.
Preferably, it is continuously evaporated under reduced pressure at vacuum degree 0.09Mpa.
Preferably, it is added in first small molecule chain extender or step 2) in step 1) and cationic hydrophilic chain extension is added
The solvent for adjusting solution concentration is added while agent, the solvent being added twice is 1~1.5：1.
Preferably, solvent is one in acetone, butanone, methyl ethyl ketone, N-Methyl pyrrolidone and n,N-Dimethylformamide
Kind is a variety of.
The effect of the solvent is to adjust the viscosity of reaction solution.The additive amount of the solvent can need to take the circumstances into consideration according to reaction
Addition.The solvent is distilled removing in the vacuum distillation stage.
The present invention selects the primary raw material of polycarbonate glycol and polycaprolactone diols as macromolecular polyol, together
When UM-90 is added, which belongs to polycarbonate glycol, and has cyclic structure on its strand, due to poly-
The presence of cyclic structure in carbonic ester dihydric alcohol, by the apparent mechanical strength for improving aqueous polyurethane glue film, wearability and resistance to
Solvent borne.Meanwhile the castor oil polyhydric alcohol of a small amount of three-functionality-degree is added, due to castor oil have long-chain fat base can be improved it is poly-
The water resistance of urethane, while castor oil hydroxyl containing there are three, can be improved the degree of cross linking of polyurethane system, to aqueous polyurethane
Comprehensive performance has larger improvement, so that not only mechanical strength is big for the modified aqueous polyurethane resin obtained, molecular weight is high, also has
Excellent water resistance energy.In addition, this method preparation is cation-type water-thinned polyurethane, due to the advantage of its positive charge, show
The adhesive force of substrate is more secured.
Silane coupling agent γ-glycidyl ether oxygen propyl trimethoxy silicane is added in the present invention in the synthesis process simultaneously,
The silane coupling agent is containing there are three the silane of silicon oxygen bond and epoxy-functional, due to the hydrolysis of silicon oxygen bond, in polyurethane system
Middle formation cross-linked network structure is remarkably improved the mechanical strength and molecular weight of film, and siloxanes is in the surface enrichment of material
The water resistance of material can be further increased, while the presence of epoxy-functional can significantly improve the adhesive property of material.
In conclusion high-performance cationic water polyurethane resin provided by the invention and preparation method thereof, beneficial
Effect is：
1. the high-performance cationic water polyurethane resin good emulsion stability that the present invention obtains, period of storage is long, should
Not only there is the film of waterborne polyurethane resin high solids content to be greater than 50%, and intensity is greater than 60MPa, and molecular weight is greater than 20W, also has
There are excellent adhesive force, water resistance, solvent resistance.
It is relatively low that 2. high-performance cation-type water-thinned polyurethane prepared by the present invention overcomes existing aqueous polyurethane solid content,
The poor defect of film performance has weight to application of the aqueous polyurethane in terms of coating, adhesive and leather finishing agent is expanded
The meaning wanted.
3. stable preparation process of the present invention reacts easily controllable, and the present invention uses biomass material castor oil part
Waterborne polyurethane resin is synthesized instead of oil polyalcohol, the utilization rate of resource not only can be improved, and can be aqueous polyurethane
Industry provides cheap raw material sources, reduces the dependence to oil product.Cost can be reduced simultaneously, to aqueous polyurethane work
The development of industry has important strategic importance.
Specific embodiment
The present invention is further explained combined with specific embodiments below, it should be appreciated that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification
Other advantages and efficacy of the present invention can be easily understood for disclosed content.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints and application, without departing from
Various modifications or alterations are carried out under spirit of the invention.
Table 1 shows each raw material component and weight in Examples 1 to 4.
Embodiment 1
A method of high-performance cationic water polyurethane resin is prepared, is included the following steps：
1) the addition 25g polycarbonate glycol into three-necked flask, 12g polycaprolactone diols, 5g castor oil, 5gUM-90,
4g1,4- cyclohexanedimethanol, add 25g toluene di-isocyanate(TDI), and 7g dipropyl dicyclohexylmethane diisocyanate is stirred, stirs
Mixing speed is 300r/min, is heated to 85 DEG C, insulation reaction 5h obtains the first performed polymer；
2) after the first performed polymer prepared by step 1) being cooled to 50 DEG C, the N methyldiethanol amine of 3g is added, keeps the temperature
1.5h obtains the second performed polymer；
3) after being cooled to 40 DEG C, 1g γ-glycidyl ether oxygen propyl trimethoxy is added into the second prepared performed polymer
Base silane reacts 10min, then adds the acetone solvent, 3g lactic acid and 100g tap water emulsion dispersion of 20g, the Isosorbide-5-Nitrae-of 4g
Hexamethylene dimethylamine continues after being stirred to react 0.5h, and vacuum distillation obtains high-performance cationic water polyurethane resin.
Each raw material component and weight in 1 Examples 1 to 4 of table
Embodiment 2
A method of high-performance cationic water polyurethane resin is prepared, is included the following steps：
1) 25g polycarbonate glycol, 12g polycaprolactone diols, 5g castor oil, 10gUM- are added into three-necked flask
90,4g1,4- cyclohexanedimethanol, add 25g toluene di-isocyanate(TDI), 7g dipropyl dicyclohexylmethane diisocyanate, and stirring mixes
It closes, mixing speed 300r/min is heated to 85 DEG C, and insulation reaction 5h obtains the first performed polymer；
2) after the first performed polymer prepared by step 1) being cooled to 50 DEG C, the N methyldiethanol amine of 3g is added, keeps the temperature
1.5h obtains the second performed polymer；
3) after being cooled to 40 DEG C, 1g γ-glycidyl ether oxygen propyl trimethoxy is added into the second prepared performed polymer
Base silane reacts 10min, then adds the acetone solvent, 3g lactic acid and 100g tap water emulsion dispersion of 20g, the Isosorbide-5-Nitrae-of 4g
Hexamethylene dimethylamine continues after being stirred to react 0.5h, and vacuum distillation obtains high-performance cationic water polyurethane resin.
Embodiment 3
A method of high-performance cationic water polyurethane resin is prepared, is included the following steps：
1) the addition 25g polycarbonate glycol into three-necked flask, 12g polycaprolactone diols, 5g castor oil, 5gUM-90,
4g1,4- cyclohexanedimethanol add 20g toluene di-isocyanate(TDI), and 12g dipropyl dicyclohexylmethane diisocyanate is stirred,
Mixing speed is 300r/min, is heated to 85 DEG C, and insulation reaction 5h obtains the first performed polymer；
2) after the first performed polymer prepared by step 1) being cooled to 50 DEG C, the N methyldiethanol amine of 3g is added, keeps the temperature
1.5h obtains the second performed polymer；
3) after being cooled to 40 DEG C, 1g γ-glycidyl ether oxygen propyl trimethoxy is added into the second prepared performed polymer
Base silane reacts 10min, then adds the acetone solvent, 3g lactic acid and 100g tap water emulsion dispersion of 20g, the Isosorbide-5-Nitrae-of 4g
Hexamethylene dimethylamine continues after being stirred to react 0.5h, and vacuum distillation obtains high-performance cationic water polyurethane resin.
Embodiment 4
A method of high-performance cationic water polyurethane resin is prepared, is included the following steps：
1) 25g polycarbonate glycol, 12g polycaprolactone diols, 5g castor oil, 10gUM- are added into three-necked flask
90,4g1,4- cyclohexanedimethanol, add 20g toluene di-isocyanate(TDI), 12g dipropyl dicyclohexylmethane diisocyanate, and stirring mixes
It closes, mixing speed 300r/min is heated to 85 DEG C, and insulation reaction 5h obtains the first performed polymer；
2) after the first performed polymer prepared by step 1) being cooled to 50 DEG C, the N methyldiethanol amine of 3g is added, keeps the temperature
1.5h obtains the second performed polymer；
3) after being cooled to 40 DEG C, 1g γ-glycidyl ether oxygen propyl trimethoxy is added into the second prepared performed polymer
Base silane reacts 10min, then adds the acetone solvent, 3g lactic acid and 100g tap water emulsion dispersion of 20g, the Isosorbide-5-Nitrae-of 4g
Hexamethylene dimethylamine continues after being stirred to react 0.5h, and vacuum distillation obtains high-performance cationic water polyurethane resin.
Performance detection：
The performance for the modified aqueous polyurethane resin lotion that embodiment 1 to 4 obtains, including emulsion appearance, solid content are detected,
The modified aqueous polyurethane emulsion that embodiment 1 to 4 is obtained carries out film, carries out glue film according to standard GB/T/1040-2006
Tensile strength test carries out glue film molecular weight test according to standard GB/T/21863-2008, according to standard GB/T/
T9286-1998 carries out adhesive force test, carries out water resistance test according to standard GB/T/T1733-1993.
The results of property for the aqueous polyurethane resin emulsion that 2 Examples 1 to 4 of table obtains
As seen from Table 1, the solid content for the aqueous polyurethane resin emulsion that embodiment 1 to 4 obtains is all larger than 50%, admittedly contain
It measures higher；The tensile strength of waterborne polyurethane resin film is all larger than 60MPa, illustrates the high mechanical strength of glue film；Aqueous poly- ammonia
The number-average molecular weight of ester resin coating film reaches 20W or more；Waterborne polyurethane resin film adhesive is 1 grade, adhesive force ratio
It is relatively strong；By tap water drop to embodiment 1 to 4 obtain modified aqueous polyurethane film on 48 hours it is without exception, illustrate that film is resistance to
It is aqueous good；So embodiment 1 to 4 obtains waterborne polyurethane resin in solid content, tensile strength, molecular weight, water resistance and attached
Put forth effort the function admirable of aspect.
The above, only presently preferred embodiments of the present invention, not to the present invention in any form with substantial limitation,
It should be pointed out that under the premise of not departing from the method for the present invention, can also be made for those skilled in the art
Several improvement and supplement, these are improved and supplement also should be regarded as protection scope of the present invention.All those skilled in the art,
Without departing from the spirit and scope of the present invention, when made using disclosed above technology contents it is a little more
Dynamic, modification and the equivalent variations developed, are equivalent embodiment of the invention；Meanwhile all substantial technologicals pair according to the present invention
The variation, modification and evolution of any equivalent variations made by above-described embodiment, still fall within the range of technical solution of the present invention
It is interior.
Claims (10)
1. a kind of high-performance cationic water polyurethane resin, which is characterized in that the resin include following raw material components and
Parts by weight：
2. a kind of high-performance cationic water polyurethane resin according to claim 1, it is characterised in that：It is described polynary
Alcohol is 45~60 parts, and the polyisocyanates is 30~38 parts, and first small molecule chain extender is 4~5 parts, the cation
Type hydrophilic chain extender is 2~3 parts, and the silane coupling agent is 1~2 part, and the salt forming agent is 2~3 parts, second small molecule
Chain extender is 3~4 parts.
3. a kind of high-performance cationic water polyurethane resin according to claim 2, it is characterised in that：It is described polynary
Alcohol is UM-90, three kinds of mixing in the pure and mild castor oil of aliphatic polyester binary.
4. a kind of high-performance cationic water polyurethane resin according to claim 3, it is characterised in that：The UM-
90, the weight ratio of the pure and mild castor oil of the aliphatic polyester binary is (4~5)：(35~45)：(6~10).
5. a kind of high-performance cationic water polyurethane resin according to claim 3, it is characterised in that：The fat
Race's polyester diol is selected from one of polycarbonate glycol and polycaprolactone diols or two kinds.
6. a kind of high-performance cationic water polyurethane resin according to claim 3, it is characterised in that：The UM-
90 structural formula is as follows：
Wherein, the integer that n is 1~1000；
Preferably, the UM-90 number-average molecular weight is 900.
7. a kind of high-performance cationic water polyurethane resin according to claim 5, it is characterised in that：The castor-oil plant
The number-average molecular weight of oil is 1000,2000,3000, preferably 2000；The number-average molecular weight of the polycarbonate glycol is
1000,2000, preferably 1000；The number-average molecular weight of the polycaprolactone diols is 1000,2000, preferably 2000.
8. a kind of high-performance cationic water polyurethane resin according to claim 2, it is characterised in that：Described two is different
It is different that cyanate is selected from toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, isophorone diisocyanate, hexa-methylene two
Any one in cyanate and dicyclohexyl diisocyanate is a variety of；First small molecule chain extender be ethylene glycol, 1,
4- butanediol, 2- methyl-1,3-propanediol, any one or more in 1,4 cyclohexane dimethanol；Second small molecule expands
Chain agent is selected from one of ethylenediamine, 1,4- hexamethylene dimethylamine, isophorone diamine or a variety of；The cationic hydrophilic chain extension
Agent is diethanol amine or N methyldiethanol amine；The salt forming agent is lactic acid.
9. a kind of high-performance cationic water polyurethane resin according to claim 2, it is characterised in that：It is silane coupled
Agent includes γ-glycidyl ether oxygen propyl trimethoxy silicane, and structural formula is：
10. a kind of method for preparing the high-performance cationic water polyurethane resin as described in claim 1~9 is any,
It is characterized in that, the described method comprises the following steps：
1) be added 40~65 parts of polyalcohol into three-necked flask, 3~5 parts of the first small molecule chain extender and 25~40 parts it is more
Isocyanates is stirred, and mixing speed is 200~500r/min, is heated to 80~90 DEG C, keeps the temperature 3~5h, obtains the
One performed polymer；
2) after the first performed polymer prepared by step 1) being cooled to 40~50 DEG C, 2~4 parts of cationic hydrophilic chain extension is added
Agent keeps the temperature 1~2h, obtains the second performed polymer；
3) 30~40 DEG C are cooled to, the silane coupling agent of 0.5~2 part of addition into the second prepared performed polymer, heat preservation 5~
Then 20min adds 20~40 parts of acetone solvent, 2~4 parts of salt forming agent, 100~120 parts of tap water and 2~4
Second small molecule chain extender of part, continues after being stirred to react 0.5~1h, is evaporated under reduced pressure, and it is cation-type water-thinned poly- to obtain high-performance
Urethane resin.
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| CN111533875A (en) * | 2020-05-07 | 2020-08-14 | 合肥科天水性科技有限责任公司 | Preparation method of cationic waterborne polyurethane, leather bottom sealing resin and leather coating |
| CN111533875B (en) * | 2020-05-07 | 2022-04-19 | 合肥科天水性科技有限责任公司 | Preparation method of cationic waterborne polyurethane, leather bottom sealing resin and leather coating |
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| CN113087954A (en) * | 2021-04-06 | 2021-07-09 | 晋江森大鞋材有限公司 | Preparation method of environment-friendly breathable polyurethane insole |
| CN115215983A (en) * | 2022-08-12 | 2022-10-21 | 山东高速集团有限公司创新研究院 | High-solid-content cationic waterborne polyurethane emulsion and preparation method thereof |
| CN117050639A (en) * | 2023-08-02 | 2023-11-14 | 浙江钰烯腐蚀控制股份有限公司 | Solvent-free modified polyurethane primer and preparation method thereof |
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