CN103640133A - Method for preparing universal or composite waterborne polyurethane condom - Google Patents
Method for preparing universal or composite waterborne polyurethane condom Download PDFInfo
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Abstract
The invention discloses a method for preparing a universal or composite waterborne polyurethane condom. The method comprises the following steps: adding diisocyanate and polytetramethylene ether glycol into acetone used as a diluent at a ratio, mixing and reacting, further adding a hydrophilic chain extender and a cross-linking modifier so as to prepare a prepolymer; further adding a neutralizer, cooling down a mixture by using icy water, adding an amine chain expander so as to obtain waterborne polyurethane emulsion, and finally manufacturing the condom by using a mold. The method has the beneficial effects that the universal or composite waterborne polyurethane condom is free of toxicity, special odor and sensitization and high in strength, can be thinned with small molecule gaps, and can be used for effectively blocking venereal diseases and the like, and meanwhile the defects that the conventional polyurethane material and a preparation method of the polyurethane material are low in elongation, high in modulus and poor in strength after the polyurethane material is made into films, moreover the method is simple, the operation is easy, the process condition is gentle, the equipment is not specially required, the condom can be produced on a conventional assembly line, and manufacturing of large scale is facilitated.
Description
Technical field
The present invention relates to the manufacturing technology of a kind of water-base polyurethane material and uses thereof, be specifically related to a kind of entirely closing or the preparation method of composite aqueous polyurethane condom.
Background technology
The making material of condom is generally natural emulsion at present, tradition natural emulsion condom has higher elasticity, good pliability, can effectively practise contraception and reduce the advantages such as infection of sexually transmitted disease, but in natural emulsion molecular structure, there is the dry between 5000 to 70000 nanometers, it is Human Sperm of 5000 nanometers etc. that these cracks can stop diameter, but when reality is used, still there are some shortcomings:
1) for the less diameter of molecule, be, the AIDS virus of 120 nanometers, the human papilloma virus between 45 nanometer to 55 nanometers, the hepatitis B of 42 nanometers etc., natural emulsion lacks the ability of blocking accordingly, medical experiment is verified, and natural emulsion condom cannot prevent the infiltration of AIDS virus etc. completely.
2), because the raw material of natural emulsion condom itself contains certain water soluble protein, cannot remove, also easily cause that human allergy reacts.
3), natural emulsion condom in the process of vulcanization reaction, can produce a kind of chemical substance of nitrosamine.Nitrosamine is a kind of carcinogen in human body, if natural emulsion condom access times are frequent, has the potential risk of induced tumor.
For this reason, people start to seek new material from synthetic material field and substitute natural emulsion and make condom.Existing science and technology is found, the synthesized polymer materials such as polyurethane, polyisoprene, Ding Qing, and its molecular structure is similar to natural emulsion, but fine and close greatly raising, its molecule space can intercept the infiltration of AIDS virus, hepatitis viruse etc. completely.
According to current disclosed technology, the preparation method (CN1218822C) that has solvent method polyurethane condom, PAUR bulging forming method (CN1142838A), the preparation method of polyether/polyester type polyurethane material and sheath thereof (CN1304944A), polyurethane rubber latex is prepared condom (CN1136054A) etc.Although the polyurethane of public technology scheme has the more unexistent excellent properties of natural emulsion, but as the material of making condom, its elastic extension rate and flexibility should seem not, and modulus is generally higher, and production method is complicated, need to dissolve, disperse, controlled condition is harsh.
Summary of the invention
The object of the invention is for provide a kind of process simple, hold manageable entirely closing or the preparation method of composite aqueous polyurethane condom.
In order to reach object of the present invention, technical scheme is as follows:
Entirely close or the preparation method of composite aqueous polyurethane condom, by mass fraction, comprise the steps:
1), prepolymerization reaction: under normal temperature, add successively in proportion 5～15% vulcabond and 12～25% polytetramethylene ether diols (PTMG), be uniformly mixed and be warmed up to 50～90 ℃, react after 2～3 hours, add 0.3～3% hydrophilic chain extender and 0.8～1.5% diluent, continue reaction 2 hours, then cool to 40～70 ℃, add again 0.3～2% cross-linked modifier and 0.5～2.7% diluent, continue reaction after 2 hours, cool to below 55 ℃, continue to add 1.3～7% diluent to adjust system viscosity and be less than 100Pas, make prepolymer;
2), emulsion process: add 0.1～2% nertralizer and 62～70% mixture of ice and water in reactor, open stirring, keep temperature of charge 5 ℃～10 ℃ of ﹣, the prepolymer making in described step 1) is added wherein, and regulate speed of agitator to 2000r/min, emulsification 10～30 minutes, adds 0.1～2% amine chainextender chain extension, and amine chainextender added with one hour, add and continue to stir one hour, make aqueous polyurethane emulsion;
3), condom fabrication processing: cleaning die → single-steeping, dry → double-steeping, dry → tri-dippings, crimping, dry → demoulding, the controlled condition of this step is specially:
1. cleaning die: mould is clean clean with clear water, control 75 ℃～80 ℃ of temperature, dry 5～15 minutes;
2. 3～15s in aqueous polyurethane emulsion single-steeping: the mould after cleaning-drying immerses described step 2 at 40～50 ℃ of temperature) making, takes out dryly, and baking temperature is 75 ℃, dry 5～20 minutes;
3. double-steeping: by 3～15s during mould is in immersing composite emulsions, control 40～50 ℃ of dipping temperatures, take out dryly, baking temperature is 75 ℃, dry 5～20 minutes;
4. three dippings: mould is immersed to described step 2 again) 3～15s in the aqueous polyurethane emulsion that makes, controls 40～50 ℃ of dipping temperatures, takes out dryly, and baking temperature is 110～120 ℃, dry 15～30 minutes;
5. after being dried, be cooled to the normal temperature demoulding, make condom finished product.
The solid content of the aqueous polyurethane emulsion as preferred technical scheme, described step 2) making is 30～38%.
The pH value of the aqueous polyurethane emulsion as preferred technical scheme, described step 2) making is 8.5～9.0.
As preferred technical scheme, in described step 3), during double-steeping, the composite emulsions of immersion is latex emulsion or described step 2) aqueous polyurethane emulsion that makes.If immerse in latex solution during double-steeping, what make is exactly composite aqueous polyurethane condom (inside and outside two-layer aqueous polyurethane, intermediate layer are latex), the existing feature that aqueous polyurethane is nontoxic, anti-virus ability is strong, retained again the good mechanical property of latex, and latex is in centre, can directly not contact with human body, therefore can not cause human allergy, can not allow the harmful substance in latex poison human body yet; If during double-steeping be equally, immersing described step 2) in the aqueous polyurethane emulsion that makes, what make is exactly full Heshui based polyurethane condom (three layers are aqueous polyurethane), and anti-virus ability is stronger.
As preferred technical scheme, described vulcabond is toluene di-isocyanate(TDI) (TDI), and described diluent is acetone.When prepolymerization reaction: under normal temperature, add successively in proportion 5～15% toluene di-isocyanate(TDI) (TDI) and 12～25% polytetramethylene ether diols (PTMG), be uniformly mixed and be warmed up to 50～60 ℃, react after 2～3 hours, add 0.3～3% hydrophilic chain extender and 0.8～1.5% diluent, continue reaction 2 hours, then cool to 40～50 ℃, add again 0.3～2% cross-linked modifier and 0.5～2.7% diluent, continue reaction after 2 hours, cool to below 55 ℃, continue to add 1.3～7% diluent to adjust system viscosity and be less than 100Pas, make prepolymer,
During emulsion process: add 0.1～2% nertralizer and 62～70% mixture of ice and water in reactor, open stirring, keep temperature of charge 5～10 ℃ of ﹣, the prepolymer making in described step 1) is added wherein, and regulate speed of agitator to 2000r/min, emulsification 10～30 minutes, add 0.1～2% amine chainextender chain extension, amine chainextender added with one hour, added and continued to stir one hour, made aqueous polyurethane emulsion.
Wherein, as preferred technical scheme, the molecular weight of described polytetramethylene ether diol (PTMG) is 1000～3000.If the molecular weight of PTMG is excessive, the thickness after aqueous polyurethane film forming is large, and elasticity and ductility are all poor, uses inconvenient; If molecular weight is too small, possibly cannot film forming.The effect of polytetramethylene ether diol is to generate ester class with unnecessary acid, guarantees that last polyaminoester emulsion is alkalescence.Described hydrophilic chain extender is any one in dihydromethyl propionic acid (DMPA) or dimethylolpropionic acid (DMBA).It is acid that hydrophilic chain extender is, and in order to regulate the acid-base value of reaction system, and guarantees that reaction system is an acid environment, is beneficial to polymerisation, because different reaction conditions can generate different types of polyurethane.Described cross-linked modifier is the mixture of any one or they in trimethylolpropane (TMP) or neopentyl glycol (NPG).The effect of cross-linked modifier is the mechanical properties such as the hot strength that improves condom, fracture strength.Described diluent is any one of acetone or dimethylacetylamide (DMAC).Described amine chainextender is diethylenetriamine.What described nertralizer was selected is NaOH or other bases, and as sodium carbonate, carbon acid sodium, potassium hydroxide or organic amine etc., the effect of nertralizer is to guarantee that the aqueous polyurethane emulsion that final reaction obtains is an alkaline environment.
In described step 1), described vulcabond is toluene di-isocyanate(TDI) (TDI), IPDI (IPDI), hydrogenated diphenyl methane diisocyanate (H
12mDI, HMDI) or hexamethylene diisocyanate (HDI) in any one or a few.
When vulcabond is TDI, be subject to the impact of himself performance, in prepolymerization reaction, and the temperature that PTMG is uniformly mixed intensification is 50～60 ℃; And when adopting IPDI, HDI or HMDI, and the temperature that PTMG is uniformly mixed intensification is 70～90 ℃.Equally, in emulsion process, while being TDI, keep temperature of charge 5～10 ℃ of ﹣ after adding mixture of ice and water, other kept temperature of charge is at 5～20 ℃.
Diluent is to be divided into repeatedly adding because along with reaction carrying out, polymerization is increasing, viscosity is more and more higher, compare disposable before reaction or reaction after add, can better stir, be beneficial to the carrying out of reaction.In addition, except hydrophilic chain extender, cross-linked modifier and diluent are added the method in system successively, also hydrophilic chain extender and cross-linked modifier can be mixed with to dilution with diluent adds again, more be conducive to slowly carrying out of reaction, prevent from too fastly reacting too fast because hydrophilic chain extender and cross-linked modifier add, generate other impurity products.
When adopting acetone as diluent, because the boiling point of acetone is lower, be cooled to 40～50 ℃ after adding hydrophilic chain extender and diluent in prepolymerization reaction, can not be over 50 ℃; And dimethylacetylamide (DMAC) is during as diluent, the temperature after cooling can remain on 40～70 ℃.
Described step 2) in, the rate of addition of amine chainextender wants slow, is controlled at about one hour and adds, if dropping is too fast, result can cause chain extension too large, polymerization.
Described step 2) effect that adds frozen water compound in is to whole reaction system cooling, reduces emulsifying temperature.This step is very crucial, because, to emulsion reaction, be reduced to suitable temperature, not only determined that aqueous polyurethane emulsion whether can film forming, also determine the physical property of aqueous polyurethane emulsion itself, and then finally had influence on the every mechanical property after film forming.If excess Temperature, can cause demulsifying phenomenon to produce, the polyaminoester emulsion obtaining, cannot film forming as bean curd shape.
Except adopting the method for mixture of ice and water, can be also first by other modes, to cool, then add water, and control reaction and carry out at required lower temperature.
The beneficial effect that the present invention has:
Compound or full Heshui based polyurethane condom prepared by the present invention, nontoxic, without special odor, high without sensitization, intensity, can be thinner, molecular gap is less, can more effectively intercept sex desease virus etc., solved that natural emulsion condom anti-virus ability is low, protein allergy, containing shortcomings such as carcinogenic nitrosamine material, the conduction of wall thickness heat are slow, have again simultaneously with latex quite, even surpass the mechanical property of latex.
Meanwhile, solved that percentage elongation is low after existing polyurethane material and preparation method thereof existing film forming, modulus is high, the defect of intensity difference.Make that percentage elongation is higher after film forming, modulus is lower, intensity is higher, can maintain good mechanical property, condom trilamellar membrane gross thickness is not more than 0.03mm, and the percentage elongation of film is not less than 980%, hot strength is not less than 1900psi, and the burst pressure of cover is not less than 1.0kPa.
Method that the present invention prepares water-base polyurethane material is simple, processing ease, process conditions are gentle, to equipment without specific (special) requirements, production safety cover can utilize conventional flow waterline to carry out, and is convenient to processing in enormous quantities.
The specific embodiment
Below in conjunction with embodiment, the invention will be further described, but protection scope of the present invention is not only confined to embodiment.
Entirely close or the preparation method of composite aqueous polyurethane condom, by mass fraction, comprise the steps:
1), prepolymerization reaction: under normal temperature, add successively in proportion 5～15% vulcabond and 12～25% polytetramethylene ether diols (PTMG), be uniformly mixed and be warmed up to 50～90 ℃, react after 2～3 hours, add 0.3～3% hydrophilic chain extender and 0.8～1.5% diluent, continue reaction 2 hours, then cool to 40～70 ℃, add again 0.3～2% cross-linked modifier and 0.5～2.7% diluent, continue reaction after 2 hours, cool to below 55 ℃, continue to add 1.3～7% diluent to adjust system viscosity and be less than 100Pas, make prepolymer;
Acetone, as diluent, is divided into repeatedly and adds because along with reaction carrying out, polymerization is increasing, viscosity is more and more higher, compare disposable before reaction or reaction after add, can better stir, be beneficial to the carrying out of reaction.
2), emulsion process: add 0.1～2% nertralizer and 62～70% mixture of ice and water in reactor, open stirring, keep temperature of charge 5 ℃～20 ℃ of ﹣, the prepolymer making in described step 1) is added wherein, and regulate speed of agitator to 2000r/min.Emulsification 10～30 minutes, adds 0.1～2% amine chainextender chain extension, and amine chainextender added with one hour, adds and continues to stir one hour, makes aqueous polyurethane emulsion;
Described step 2) in, the rate of addition of amine chainextender wants slow, is controlled at about one hour and adds, if dropping is too fast, result can cause chain extension too large, polymerization.
Described step 2) effect that adds frozen water compound in is to whole reaction system cooling, reduces emulsifying temperature.This step is very crucial, because, to emulsion reaction, be reduced to suitable temperature, not only determined that aqueous polyurethane emulsion whether can film forming, also determine the physical property of aqueous polyurethane emulsion itself, and then finally had influence on the every mechanical property after film forming.If excess Temperature, can cause demulsifying phenomenon to produce, the polyaminoester emulsion obtaining, cannot film forming as bean curd shape.
Except adopting the method for mixture of ice and water, can be also first by other modes, to cool, then add water, and control reaction and carry out at required lower temperature.
3), condom fabrication processing: cleaning die → single-steeping, dry → double-steeping, dry → tri-dippings, crimping, dry → demoulding, the controlled condition of this step is specially:
1. cleaning die: mould is clean clean with clear water, control 75 ℃～80 ℃ of temperature, dry 5～15 minutes;
2. 3～15s in aqueous polyurethane emulsion single-steeping: the mould after cleaning-drying immerses described step 2 at 40～50 ℃ of temperature) making, takes out dryly, and baking temperature is 75 ℃, dry 5～20 minutes;
3. double-steeping: by 3～15s during mould is in immersing composite emulsions, control 40～50 ℃ of dipping temperatures, take out dryly, baking temperature is 75 ℃, dry 5～20 minutes;
4. three dippings: mould is immersed to described step 2 again)) 3～15s in the aqueous polyurethane emulsion that makes, controls 40～50 ℃ of dipping temperatures, takes out dryly, and baking temperature is 110～120 ℃, dry 15～30 minutes;
5. after being dried, be cooled to the normal temperature demoulding, make condom finished product.
The solid content of the aqueous polyurethane emulsion described step 2) making is 30～38%.The pH value of the aqueous polyurethane emulsion described step 2) making is 8.5～9.0.
In described step 3), during double-steeping, the composite emulsions of immersion is latex emulsion or described step 2) aqueous polyurethane emulsion that makes.If immerse in latex solution during double-steeping, what make is exactly composite aqueous polyurethane condom (inside and outside two-layer aqueous polyurethane, intermediate layer are latex), the existing feature that aqueous polyurethane is nontoxic, anti-virus ability is strong, has retained again the good mechanical property of latex; If during double-steeping be equally, immersing described step 2) in the aqueous polyurethane emulsion that makes, what make is exactly full Heshui based polyurethane condom (three layers are aqueous polyurethane), and anti-virus ability is more strengthened.
Embodiment 1:
Prepolymerization reaction: under normal temperature, in the reactor stirring to band, add the polytetramethylene ether diol (PTMG) that 122g toluene di-isocyanate(TDI) (TDI) and 120g molecular weight are 1000, be uniformly mixed and be warmed up to 50～60 ℃, react after 2 hours, add 3gDMPA and 10g acetone, continue reaction 2 hours, then cool to 40～50 ℃, adding concentration is that the acetone diluted liquid 30g(of 10% neopentyl glycol and trimethylolpropane mixture is that the quality of neopentyl glycol and trimethylolpropane mixture is 3g again, acetone is 27g), continue reaction after 2 hours, cool to below 55 ℃, add 13g acetone to adjust system viscosity and be less than 100Pas, make prepolymer.
Emulsion process: add 1gNaOH and 691g mixture of ice and water in 1000ml reactor, open stirring, keep 5 ℃～0 ℃ of temperature of charge ﹣, slowly prepolymer is added wherein, add rear rapid raising speed of agitator to 2000r/min.Emulsification 10 minutes, adds the diethylenetriamine aqueous solution chain extension of 10g content 10%, and the diethylenetriamine aqueous solution slowly drips and use within one hour, add, and adds and continues to stir one hour, makes the condom use polyaminoester emulsion of solid content 30%.
Condom fabrication processing:
1. cleaning die: mould is clean clean with clear water, control 75 ℃ of temperature, dry 5～15 minutes.
2. single-steeping: the mould after cleaning-drying immerses 3～15s in the aqueous polyurethane emulsion that above-mentioned steps two make 40～50 ℃ of temperature, takes out dry.Baking temperature is 75 ℃, dry 5～20 minutes.
3. double-steeping: repeat above-mentioned steps operating process 2..
4. flood for three times: control 40～50 ℃ of dipping temperatures, dipping emulsion time 3～15s, crimping, baking temperature is 110～120 ℃, dry 15～30 minutes.
5. after being dried, be cooled to the normal temperature demoulding, make condom finished product, and the internal layer of this condom, intermediate layer and outer field material be aqueous polyurethane.
Embodiment 2:
Prepolymerization reaction is identical with the step of above-described embodiment 1 with emulsion process, just, in the double-steeping when condom is made, immerses in latex emulsion, and making internal layer and outer field material is aqueous polyurethane, and the material in intermediate layer is latex.
Embodiment 3:
Prepolymerization reaction: under normal temperature, in the reactor stirring to band, add the polytetramethylene ether diol (PTMG) that 70g hydrogenated diphenyl methane diisocyanate (HMDI) and 120g molecular weight are 3000, be uniformly mixed and be warmed up to 90 ℃, react after 2 hours, adding 40g mass fraction is 75% dimethylolpropionic acid (DMBA) acetone soln, continue reaction 2 hours, then cool to 50 ℃, adding mass fraction is that the acetone diluted liquid 40g(of 50% neopentyl glycol and trimethylolpropane mixture is that the quality of neopentyl glycol and trimethylolpropane mixture is 20g again, acetone is 20g), continue reaction after 2 hours, cool to below 55 ℃, add 70g acetone to adjust system viscosity and be less than 100Pas, make prepolymer.
Emulsion process: add 20gNaOH and 440g mixture of ice and water in 1000ml reactor, open stirring, keep 15 ℃～20 ℃ of temperature of charge, slowly prepolymer is added wherein, add rear rapid raising speed of agitator to 2000r/min.Emulsification 30 minutes, adds the diethylenetriamine aqueous solution chain extension of 200g content 10%, and the diethylenetriamine aqueous solution slowly drips and use within one hour, add, and adds and continues to stir one hour, makes the condom use polyaminoester emulsion of solid content 31.5%.
Condom fabrication processing:
With embodiment 1.
Embodiment 4:
Prepolymerization reaction: under normal temperature, in the reactor stirring to band, add the polytetramethylene ether diol (PTMG) that 150g IPDI (IPDI) and 120g molecular weight are 2000, be uniformly mixed and be warmed up to 85 ℃, react after 2 hours, adding 20g mass fraction is 50% dimethylolpropionic acid (DMBA) acetone soln, continue reaction 2 hours, then cool to 60～70 ℃, adding mass fraction is that the acetone diluted liquid 20g(of 50% neopentyl glycol and trimethylolpropane mixture is that the quality of neopentyl glycol and trimethylolpropane mixture is 10g again, acetone is 10g), continue reaction after 2 hours, cool to below 55 ℃, add 50g acetone to adjust system viscosity and be less than 100Pas, make prepolymer.
Emulsion process: add 10gNaOH and 530g mixture of ice and water in 1000ml reactor, open stirring, keep 10 ℃～15 ℃ of temperature of charge, slowly prepolymer is added wherein, add rear rapid raising speed of agitator to 2000r/min.Emulsification 20 minutes, adds the diethylenetriamine aqueous solution chain extension of 100g content 10%, and the diethylenetriamine aqueous solution slowly drips and use within one hour, add, and adds and continues to stir one hour, makes the condom use polyaminoester emulsion of solid content 31%.
Condom fabrication processing:
With embodiment 1.
Embodiment 5:
Prepolymerization reaction: under normal temperature, in the reactor stirring to band, add 28g methyl diphenylene diisocyanate (HMDI), the polytetramethylene ether diol (PTMG) that 28 hexamethylene diisocyanates (HDI) and 250g molecular weight are 2500, be uniformly mixed and be warmed up to 70 ℃, react after 2 hours, adding 16g mass fraction is 50% dimethylolpropionic acid (DMBA) acetone soln, continue reaction 2 hours, then cool to 55 ℃, adding mass fraction is that the acetone diluted liquid 12g(of 50% neopentyl glycol and trimethylolpropane mixture is that the quality of neopentyl glycol and trimethylolpropane mixture is 6g again, acetone is 6g), continue reaction after 2 hours, cool to below 55 ℃, add 36g acetone to adjust system viscosity and be less than 100Pas, make prepolymer.
Emulsion process: add 5gNaOH and 575g mixture of ice and water in 1000ml reactor, open stirring, keep 5 ℃～10 ℃ of temperature of charge, slowly prepolymer is added wherein, add rear rapid raising speed of agitator to 2000r/min.Emulsification 15 minutes, adds the diethylenetriamine aqueous solution chain extension of 50g content 10%, and the diethylenetriamine aqueous solution slowly drips and use within one hour, add, and adds and continues to stir one hour, makes the condom use polyaminoester emulsion of solid content 30%.
Condom fabrication processing:
With embodiment 1.
Embodiment 6:
Prepolymerization reaction: under normal temperature, in the reactor stirring to band, add 50g toluene di-isocyanate(TDI) (TDI), the polytetramethylene ether diol (PTMG) that 50 hexamethylene diisocyanates (HDI) and 250g molecular weight are 1500, be uniformly mixed and be warmed up to 75 ℃, react after 2 hours, adding 30g mass fraction is 50% dimethylolpropionic acid (DMBA) acetone soln, continue reaction 2 hours, then cool to 60 ℃, adding mass fraction is that the acetone diluted liquid 10g(of 50% neopentyl glycol and trimethylolpropane mixture is that the quality of neopentyl glycol and trimethylolpropane mixture is 5g again, acetone is 5g), continue reaction after 2 hours, cool to below 55 ℃, add 36g acetone to adjust system viscosity and be less than 100Pas, make prepolymer.
Emulsion process: add 15gNaOH and 485g mixture of ice and water in 1000ml reactor, open stirring, keep 5 ℃～10 ℃ of temperature of charge, slowly prepolymer is added wherein, add rear rapid raising speed of agitator to 2000r/min.Emulsification 25 minutes, adds the diethylenetriamine aqueous solution chain extension of 150g content 10%, and the diethylenetriamine aqueous solution slowly drips and use within one hour, add, and adds and continues to stir one hour, makes the condom use polyaminoester emulsion of solid content 30%.
Condom fabrication processing:
With embodiment 1.
Embodiment 7:
Prepolymerization reaction is identical with the step of above-described embodiment 5 with emulsion process, just, in the double-steeping when condom is made, immerses in latex, and making internal layer and outer field material is aqueous polyurethane, and the material in intermediate layer is latex.
Embodiment 8:
Prepolymerization reaction is identical with the step of above-described embodiment 6 with emulsion process, just, in the double-steeping when condom is made, immerses in latex, and making internal layer and outer field material is aqueous polyurethane, and the material in intermediate layer is latex.
The condom that above each embodiment is made and the condom of commercially available two kinds of samples carries out material and performance detects, testing standard is carried out according to GB7544-1992, GB/T7546-1992 and GB/T7547-1992, and test result is as shown in following table 1 and 2:
100% modulus, modulus when being stretched to 100% exactly; 300% modulus, modulus when being stretched to 300% exactly.Modulus is larger, and elasticity is less.
Fracture strength, refers to that the stress of fracture occurs material, and the ratio of the length of extending till during fracture and the length of sample itself is percentage elongation (%).
The material-structure of each condom of table 1
| ? | Thickness mm | Internal layer | Intermediate layer | Outer |
| Embodiment 1 | 0.03 | Aqueous polyurethane | Aqueous polyurethane | Aqueous polyurethane |
| Embodiment 2 | 0.03 | Aqueous polyurethane | Latex | Aqueous polyurethane |
| Embodiment 3 | 0.03 | Aqueous polyurethane | Aqueous polyurethane | Aqueous polyurethane |
| Embodiment 4 | 0.03 | Aqueous polyurethane | Aqueous polyurethane | Aqueous polyurethane |
| Embodiment 5 | 0.03 | Aqueous polyurethane | Aqueous polyurethane | Aqueous polyurethane |
| Embodiment 6 | 0.03 | Aqueous polyurethane | Aqueous polyurethane | Aqueous polyurethane |
| Embodiment 7 | 0.03 | Aqueous polyurethane | Latex | Aqueous polyurethane |
| Embodiment 8 | 0.03 | Aqueous polyurethane | Latex | Aqueous polyurethane |
| Commercially available sample 1 | 0.03 | Latex | Latex | Latex |
| Commercially available sample 2 | 0.03 | Latex | Latex | Latex |
Each the performance test results of table 2 condom
Remarks: (psi=pound/square inch)
From table 1 and table 2:
Compound or the full Heshui based polyurethane condom that uses the inventive method to prepare, nontoxic, without special odor, high without sensitization, intensity, can be thinner, molecular gap is less, can more effectively intercept sex desease virus etc., solved that natural emulsion condom anti-virus ability is low, protein allergy, containing shortcomings such as carcinogenic nitrosamine material, the conduction of wall thickness heat are slow, have again simultaneously with latex quite, even surpass the mechanical property of latex.
Meanwhile, solved that percentage elongation is low after existing polyurethane material and preparation method thereof existing film forming, modulus is high, the defect of intensity difference.Make that percentage elongation is higher after film forming, modulus is lower, intensity is higher, can maintain good mechanical property, condom trilamellar membrane gross thickness is not more than 0.03mm, and the percentage elongation of film is not less than 980%, hot strength is not less than 1900psi, and the burst pressure of cover is not less than 1.0kPa.
Method that the present invention prepares water-base polyurethane material is simple, processing ease, process conditions are gentle, to equipment without specific (special) requirements, production safety cover can utilize conventional flow waterline to carry out, and is convenient to processing in enormous quantities.
Finally it should be noted that: above embodiment is only in order to illustrate the present invention and unrestricted technical scheme described in the invention, therefore, although this description has been described in detail the present invention with reference to each above-mentioned embodiment, but, those of ordinary skill in the art is to be understood that, still can modify or be equal to replacement the present invention, and all do not depart from technical scheme and the improvement thereof of the spirit and scope of the present invention, it all should be encompassed in claim scope of the present invention.
Claims (7)
1. entirely close or the preparation method of composite aqueous polyurethane condom, by mass fraction, it is characterized in that: comprise the steps:
1), prepolymerization reaction: under normal temperature, add successively in proportion 5～15% vulcabond and 12～25% polytetramethylene ether diols, be uniformly mixed and be warmed up to 50～90 ℃, react after 2～3 hours, add 0.3～3% hydrophilic chain extender and 0.8～1.5% diluent, continue reaction 2 hours, then cool to 40～70 ℃, add again 0.3～2% cross-linked modifier and 0.5～2.7% diluent, continue reaction after 2 hours, cool to below 55 ℃, continue to add 1.3～7% diluent to adjust system viscosity and be less than 100Pas, make prepolymer;
2), emulsion process: add 0.1～2% nertralizer and 62～70% mixture of ice and water in reactor, open stirring, keep temperature of charge 5 ℃～20 ℃ of ﹣, the prepolymer making in described step 1) is added wherein, and regulate speed of agitator to 2000r/min, emulsification 10～30 minutes, adds 0.1～2% amine chainextender chain extension, and amine chainextender added with one hour, add and continue to stir one hour, make aqueous polyurethane emulsion;
3), condom fabrication processing: cleaning die → single-steeping, dry → double-steeping, dry → tri-dippings, crimping, dry → demoulding, the controlled condition of this step is specially:
1. cleaning die: mould is clean clean with clear water, control 75 ℃～80 ℃ of temperature, dry 5～15 minutes;
2. 3～15s in aqueous polyurethane emulsion single-steeping: the mould after cleaning-drying immerses described step 2 at 40～50 ℃ of temperature) making, takes out dryly, and baking temperature is 75 ℃, dry 5～20 minutes;
3. double-steeping: by 3～15s during mould is in immersing composite emulsions, control 40～50 ℃ of dipping temperatures, take out dryly, baking temperature is 75 ℃, dry 5～20 minutes;
4. three dippings: mould is immersed to described step 2 again)) 3～15s in the aqueous polyurethane emulsion that makes, controls 40～50 ℃ of dipping temperatures, takes out dryly, and baking temperature is 110～120 ℃, dry 15～30 minutes;
5. after being dried, be cooled to the normal temperature demoulding, make condom finished product.
2. according to claim 1 entirely closing or the preparation method of composite aqueous polyurethane condom, is characterized in that described step 2) percentage by weight of the solid content of the aqueous polyurethane emulsion that makes is 30～38%.
3. according to claim 1 entirely closing or the preparation method of composite aqueous polyurethane condom, is characterized in that described step 2) the pH value of the aqueous polyurethane emulsion that makes is 8.5～9.0.
4. according to claim 1 entirely closing or the preparation method of composite aqueous polyurethane condom, it is characterized in that, in described step 3), during double-steeping, the composite emulsions of immersion is latex emulsion or described step 2) aqueous polyurethane emulsion that makes.
5. according to claim 1 entirely closing or the preparation method of composite aqueous polyurethane condom, is characterized in that, described vulcabond is toluene di-isocyanate(TDI).
6. according to claim 5 entirely closing or the preparation method of composite aqueous polyurethane condom, is characterized in that, described diluent is acetone.
7. according to claim 6 entirely closing or the preparation method of composite aqueous polyurethane condom, it is characterized in that, when prepolymerization reaction: under normal temperature, add successively in proportion 5～15% toluene di-isocyanate(TDI) and 12～25% polytetramethylene ether diols, be uniformly mixed and be warmed up to 50～60 ℃, react after 2～3 hours, add 0.3～3% hydrophilic chain extender and 0.8～1.5% diluent, continue reaction 2 hours, then cool to 40～50 ℃, add again 0.3～2% cross-linked modifier and 0.5～2.7% diluent, continue reaction after 2 hours, cool to below 55 ℃, continue to add 1.3～7% diluent to adjust system viscosity and be less than 100Pas, make prepolymer,
During emulsion process: add 0.1～2% nertralizer and 62～70% mixture of ice and water in reactor, open stirring, keep temperature of charge 5～10 ℃ of ﹣, the prepolymer making in described step 1) is added wherein, and regulate speed of agitator to 2000r/min, emulsification 10～30 minutes, add 0.1～2% amine chainextender chain extension, amine chainextender added with one hour, added and continued to stir one hour, made aqueous polyurethane emulsion.
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| CN104339485A (en) * | 2014-10-23 | 2015-02-11 | 中国化工株洲橡胶研究设计院有限公司 | Production method of polyurethane latex condom and special mold thereof |
| CN104840295A (en) * | 2015-05-22 | 2015-08-19 | 上海强睿博化工有限公司 | Novel polyurethane condom and method for manufacturing same |
| CN105034225A (en) * | 2015-09-02 | 2015-11-11 | 上海强睿博化工有限公司 | Condom demoulding method |
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| CN104840295A (en) * | 2015-05-22 | 2015-08-19 | 上海强睿博化工有限公司 | Novel polyurethane condom and method for manufacturing same |
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