CN101633629B - Polyurethane cross-linking agent and application thereof for preparing cross-linked aquagel - Google Patents
Polyurethane cross-linking agent and application thereof for preparing cross-linked aquagel Download PDFInfo
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- CN101633629B CN101633629B CN200910183002A CN200910183002A CN101633629B CN 101633629 B CN101633629 B CN 101633629B CN 200910183002 A CN200910183002 A CN 200910183002A CN 200910183002 A CN200910183002 A CN 200910183002A CN 101633629 B CN101633629 B CN 101633629B
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- AUBOCPGIGWSTNB-UHFFFAOYSA-N CC1CC(C)(C)CC(C)(C)C1 Chemical compound CC1CC(C)(C)CC(C)(C)C1 AUBOCPGIGWSTNB-UHFFFAOYSA-N 0.000 description 1
- GWHJZXXIDMPWGX-UHFFFAOYSA-N Cc1ccc(C)c(C)c1 Chemical compound Cc1ccc(C)c(C)c1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a polyurethane cross-linking agent which is a polyurethane prepolymer. The polyurethane cross-linking agent has a following structural formula R2-OCNH-R1-NHCO-R2, wherein m=0-5 and n=1-20. The polyurethane cross-linking agent can be used for preparing aquagel. The polyurethane perpolymer is adopted as the cross-linking agent, and the common free radical solution is polymerized to prepare the aquagel. The molecular weight of allyl alcohol ether is regulated so as to regulate the structure of the polyurethane cross-linking agent, the intensity of the aquagel can be changed according to requirements, the use quantity of the polyurethane cross-linking agent is controlled to change the cross-linked network density of the aquagel, and to improve the swelling degree, the swelling rate, and the like of the aquagel, which are key indexes of the aquagel to decide specific purposes.
Description
Technical field
The present invention relates to a kind of polyurethane cross-linking agent and as linking agent in the application of preparation in the hydrogel.
Background technology
Hydrogel (Hydrogel) is a kind of macromolecule network system, and character is soft, can keep certain shape, can swelling in water, can not dissolve, and with tissue and similar, have broad application prospects in fields such as biology, medical science and pharmaceutical prepns.As the high water-keeping material of a kind of high suction; Hydrogel is widely used in multiple field, as: the drought resisting of dry, the dewfall in agricultural film, the building prevent the water blockoff adjustment in agent, humextant, the petrochemical complex; The dehydration of crude oil or processed oil; Dust-inhibitor in mining industry, the preservation agent in the food, thickening material, pharmaceutical carrier in the medical treatment or the like.
Every water-soluble or hydrophilic polymer through certain chemically crosslinked or physical crosslinking, can form hydrogel.These polymers can be divided into natural and synthetic two big types by its source.Natural hydrophilic macromolecule comprises polyose (starch, Mierocrystalline cellulose, Lalgine, mucinase, chitosan etc.) and polypeptide class (collagen, gather L-Methionin, gather L-L-GLUTAMICACID etc.).The synthetic hydrophilic high mol comprises ROHM, SEPIGEL 305 and derivatives class thereof (SEPIGEL 305, poly N-isopropyl acrylamide gathers N-and gathers for acrylic amide etc. for ROHM, polymethyl acrylic acid).
The synthetic hydrogel generally reacts under the initiator effect through vinyl monomer and linking agent and makes.Tang Liming etc. have synthesized serial both sexes hydrogel through the crosslinking copolymerization of acrylate-based client anionic polyurethane (PU) with methylacryoyloxyethyl benzyl dimethyl ammonium chloride; Introduce among the patent CN1228447 and adopt N, N-ethylene bisacrylamide is as linking agent, and an amount of acrylic amide, catalyzer, accelerator are distributed to promotor and carry out the hydrogel that polyreaction prepares different degree of crosslinking and concentration in the zero(ppm) water medium.Patent CN1439675 discloses a kind of medical acrylic acid copolymer aquagel, and it adopts the multipolymer of acrylic amide, crylic acid hydroxy ester or methylacrylic acid hydroxyl ester and linking agent and de-ionized pure water to form, and linking agent is N; N-methylene diacrylamide or N; N-pentamethylene bisacrylamide, or dimethacrylate glycerine ester, or TGM 1; Or N, N-diallyl tartrate diamide.Announced among the patent US2007020226 and adopted acrylic amide and methylene-bisacrylamide to synthesize a kind of stable hydrogel.
The present invention has adopted a kind of novel polyurethane cross-linking agent, and this linking agent carries out free radical solution polymerization with vinyl monomer again through the base polyurethane prepolymer for use as of allyl alcohol ether, the synthetic terminal double bond of isocyanic ester under the initiator effect, synthesized a kind of stable hydrogel.
Summary of the invention
The purpose of this invention is to provide a kind of new polyurethane linking agent and be applied to prepare the method for hydrogel.Through adjusting, can improve the intensity of hydrogel to allyl alcohol ether molecular weight; Adjustment base polyurethane prepolymer for use as consumption can change hydrogel cross-linked network density, therefore can be according to hydrogel intensity, flexible concrete needs are adjusted.
Technical scheme of the present invention is following:
A kind of polyurethane cross-linking agent, it is a kind of base polyurethane prepolymer for use as, it has following general structure:
R
2—OOCNH—R
1—NHCOO—R
2
Wherein:
Wherein: m=0～5, n=1～20.
A kind of method for preparing above-mentioned polyurethane cross-linking agent, it is made up of the following step:
Step 1. vinyl carbinol polyoxytrimethylene polyoxyethylene ether is heated to 110～120 ℃ and vacuumizes dehydration 1-2 hour in reaction vessel; Be cooled to normal temperature; The polymerization degree of polyoxytrimethylene is 0-5 in the described vinyl carbinol polyoxytrimethylene polyoxyethylene ether, and the polymerization degree of polyoxyethylene is 1-20;
Step 2. adds tolylene diisocyanate (TDI) or isophorone diisocyanate at normal temperatures in reaction vessel, reacted 0.5-1 hour;
Step 3. is warming up to 50-70 ℃ then, reacts 3-6 hour, obtains polyurethane cross-linking agent.
The method for making of above-mentioned polyurethane cross-linking agent, the add-on of described tolylene diisocyanate or isophorone diisocyanate are them with the ratio of the amount of substance of vinyl carbinol polyoxytrimethylene polyoxyethylene ether is 1.0 to compare 1.0-1.1.
The above-mentioned polyurethane cross-linking agent of a kind of usefulness prepares the method for hydrogel, and it is made up of the following step:
Be dissolved in after step 1. is mixed vinyl monomer, polyurethane cross-linking agent and initiator and process reaction system in the solvent; The mass ratio of each composition is in this system: monomer: linking agent: initiator: solvent=100: 1～50: 0.2～2: 100～1000; Described vinyl monomer is acrylic amide, N hydroxymethyl acrylamide, vinylformic acid or Hydroxyethyl acrylate, or their any mixtures of the two; Described initiator is ammonium persulphate or Potassium Persulphate, and described solvent is the mixed solvent that water, ethanol and acetone are formed,
Step 2. is reacted the reaction system of step 1 3～24 hours at 35～75 ℃, makes thick hydrogel,
The thick hydrogel stripping and slicing that step 3. makes step 2 is fully soaked, is washed, and vacuum-drying is again pulverized, and is mixed with required hydrogel with an amount of zero(ppm) water.
Its reaction process example is (is example with tolylene diisocyanate TDI and acrylic amide) as follows:
Wherein:
Characteristics of the present invention and effect
Adopt base polyurethane prepolymer for use as of the present invention as linking agent, just can make hydrogel through the conventional free radical solution polymerization.Regulate the molecular weight of allyl alcohol ether, just adjust the polyurethane cross-linking agent structure, can change hydrogel intensity as required; Control polyurethane cross-linking agent consumption can change hydrogel cross-linked network density, performances such as the degree of swelling of improvement hydrogel, swelling rate, and this is some key indexs of hydrogel, has determined its concrete purposes.
The physicochemical property of urethane crosslinks hydrogel of the present invention is following:
(1) outward appearance: transparent, colourless hydrogel;
(2) pH value: 7.0～7.5;
(3) chemical structure is identified (IR): crosslink propylene acid amides or cross-linked acrylic acid;
(4) 220 ℃ of DSC DTA of thermostability are not found to change;
(5) chemicalstability: boiling water boils back IR and identifies that chemical structure does not change.
Embodiment
The preparation of embodiment 1. polyurethane cross-linking agents
In four there-necked flasks, add respectively 200g allyl alcohol ether a (vinyl carbinol-polyoxytrimethylene polyoxyethylene ether, wherein: m=1, n=2; Down together), vacuumize 1～2h, be cooled to normal temperature 110～120 ℃ of dehydrations; Respectively add 87g at normal temperatures, tolylene diisocyanate (TDI) reaction 0.5～1h is warming up to 50～70 ℃; Reaction 3～6h obtains polyurethane cross-linking agent A.
The preparation of embodiment 2. polyurethane cross-linking agents
In four there-necked flasks, add respectively 200g allyl alcohol ether b (vinyl carbinol-polyoxytrimethylene polyoxyethylene ether, wherein: m=0, n=8; Down together), vacuumize 1～2h, be cooled to normal temperature 110～120 ℃ of dehydrations; Respectively add 55.5g at normal temperatures, isophorone diisocyanate (IPDI) reaction 0.5～1h is warming up to 50～70 ℃; Reaction 3～6h obtains polyurethane cross-linking agent B.
The preparation of embodiment 3. polyurethane cross-linking agents
In four there-necked flasks, add 200g allyl alcohol ether b respectively, vacuumize 1～2h, be cooled to normal temperature 110～120 ℃ of dehydrations; Respectively add 43.5g at normal temperatures, tolylene diisocyanate (TDI) reaction 0.5～1h is warming up to 50～70 ℃; Reaction 3～6h obtains polyurethane cross-linking agent C respectively.
The preparation of embodiment 4. polyurethane cross-linking agents
In four there-necked flasks, add respectively 200g allyl alcohol ether c (vinyl carbinol-polynary ether of polyoxytrimethylene polyoxyethylene, wherein: m=3, n=4; Down together), vacuumize 1～2h, be cooled to normal temperature 110～120 ℃ of dehydrations; Respectively add 55.5g at normal temperatures, isophorone diisocyanate (IPDI) reaction 0.5～1h is warming up to 50～70 ℃; Reaction 3～6h obtains polyurethane cross-linking agent D respectively.
The preparation of embodiment 5. polyurethane cross-linking agents
In four there-necked flasks, add respectively 200g allyl alcohol ether d (vinyl carbinol-polyoxytrimethylene polyoxyethylene ether, wherein: m=0, n=16; Down together), vacuumize 1～2h, be cooled to normal temperature 110～120 ℃ of dehydrations; Respectively add 21.8g tolylene diisocyanate (TDI) reaction 0.5～1h at normal temperatures; Be warming up to 50～70 ℃, reaction 3～6h obtains polyurethane cross-linking agent E respectively.
The preparation of embodiment 6. polyurethane cross-linking agents
In four there-necked flasks, add 200g allyl alcohol ether d respectively; Vacuumize 1～2h 110～120 ℃ of dehydrations; Be cooled to normal temperature, respectively add 27.8g isophorone diisocyanate (IPDI) reaction 0.5～1h at normal temperatures, be warming up to 50～70 ℃; Reaction 3～6h obtains polyurethane cross-linking agent F respectively.
The preparation of embodiment 7. hydrogels
8.75g acrylic amide, the 1gN-NMA, 0.25g polyurethane cross-linking agent A and 0.05g ammonium persulphate are dissolved in 35ml water/ethanol/acetone (15: 3: 2v/v/v); Thorough mixing is even, with nitrogen replacement at least 3 times, seals; Place 40 ℃ of water bath with thermostatic control 6h, the hydrogel that obtains.With the gel stripping and slicing that forms, fully to soak, wash, vacuum-drying is again pulverized, and is mixed with required hydrogel with an amount of zero(ppm) water.
The preparation of embodiment 8. hydrogels
9.5g acrylic amide, 0.5g polyurethane cross-linking agent B and 0.05g ammonium persulphate are dissolved in 35ml water/ethanol/acetone (15: 3: 2 v/v/v), thorough mixing is even; With nitrogen replacement at least 3 times, seal, place 40 ℃ of water bath with thermostatic control 6h; Obtain hydrogel with the gel stripping and slicing that forms, fully soak, wash vacuum-drying again; Pulverize, be mixed with required hydrogel with an amount of zero(ppm) water.
The preparation of embodiment 9. hydrogels
9.5g acrylic amide, 0.5g polyurethane cross-linking agent C and 0.05g ammonium persulphate are dissolved in 35ml water/ethanol/acetone (15: 3: 2 v/v/v), thorough mixing is even; With nitrogen replacement at least 3 times, seal, place 40 ℃ of water bath with thermostatic control 6h; Obtain hydrogel with the gel stripping and slicing that forms, fully soak, wash vacuum-drying again; Pulverize, be mixed with required hydrogel with an amount of zero(ppm) water.
The preparation of embodiment 10. hydrogels
9g acrylic amide, 1g polyurethane cross-linking agent C and 0.05g ammonium persulphate are dissolved in 35ml water/ethanol/acetone (15: 3: 2 v/v/v), and thorough mixing is even; With nitrogen replacement at least 3 times, seal, place 40 ℃ of water bath with thermostatic control 6h; Obtain hydrogel with the gel stripping and slicing that forms, fully soak, wash vacuum-drying again; Pulverize, be mixed with required hydrogel with an amount of zero(ppm) water.
The preparation of embodiment 11. hydrogels
9.5g vinylformic acid, 2g Hydroxyethyl acrylate, 0.5g polyurethane cross-linking agent A and 0.05g Potassium Persulphate are dissolved in 35ml water/ethanol/acetone (15: 3: 2 v/v/v); Thorough mixing is even, with nitrogen replacement at least 3 times, seals; Place 50 ℃ of water bath with thermostatic control 6h, obtain hydrogel, fully soak, wash the gel stripping and slicing that forms; Vacuum-drying is again pulverized, and is mixed with required hydrogel with an amount of zero(ppm) water.
The preparation of embodiment 12. hydrogels
9g vinylformic acid, 1g polyurethane cross-linking agent D and 0.05g Potassium Persulphate are dissolved in 35ml water/ethanol/acetone (15: 3: 2 v/v/v), and thorough mixing is even; With nitrogen replacement at least 3 times, seal, place 50 ℃ of water bath with thermostatic control 6h; Obtain hydrogel with the gel stripping and slicing that forms, fully soak, wash vacuum-drying again; Pulverize, be mixed with required hydrogel with an amount of zero(ppm) water.
The preparation of embodiment 13. hydrogels
9g vinylformic acid, 1g polyurethane cross-linking agent E and 0.05g Potassium Persulphate are dissolved in 35ml water/ethanol/acetone (15: 3: 2 v/v/v), and thorough mixing is even; With nitrogen replacement at least 3 times, seal, place 50 ℃ of water bath with thermostatic control 6h; Obtain hydrogel with the gel stripping and slicing that forms, fully soak, wash vacuum-drying again; Pulverize, be mixed with required hydrogel with an amount of zero(ppm) water.
The preparation of embodiment 14. hydrogels
9g vinylformic acid, 1g polyurethane cross-linking agent F and 0.05g Potassium Persulphate are dissolved in 35ml water/ethanol/acetone, and (15: 3: 2v/v/v), thorough mixing was even; With nitrogen replacement at least 3 times, seal, place 50 ℃ of water bath with thermostatic control 6h; Obtain hydrogel with the gel stripping and slicing that forms, fully soak, wash vacuum-drying again; Pulverize, be mixed with required hydrogel with an amount of zero(ppm) water.
Claims (3)
1. polyurethane cross-linking agent, it is a kind of base polyurethane prepolymer for use as, it is characterized in that it has following general structure:
R
2-OCNH-R
1-NHCO-R
2
Wherein:
2. method for preparing the described polyurethane cross-linking agent of claim 1 is characterized in that it is made up of the following step:
Step 1. vinyl carbinol polyoxytrimethylene polyoxyethylene ether is heated to 110～120 ℃ and vacuumizes dehydration 1-2 hour in reaction vessel; Be cooled to normal temperature; The polymerization degree of polyoxytrimethylene is 0-5 in the described vinyl carbinol polyoxytrimethylene polyoxyethylene ether, and the polymerization degree of polyoxyethylene is 1-20;
Step 2. adds isophorone diisocyanate at normal temperatures in the reaction vessel of step 1, reacted 0.5-1 hour;
Step 3. is warming up to 50-70 ℃ then, reacts 3-6 hour, obtains polyurethane cross-linking agent.
3. one kind prepares the method for hydrogel with the described polyurethane cross-linking agent of claim 1, it is characterized in that it is made up of the following step:
Be dissolved in after step 1. is mixed vinyl monomer, polyurethane cross-linking agent and initiator and process reaction system in the solvent; The mass ratio of each composition is in this system: monomer: linking agent: initiator: solvent=100: 1～50: 0.2～2: 100～1000; Described vinyl monomer is acrylic amide, N hydroxymethyl acrylamide, vinylformic acid or Hydroxyethyl acrylate, or their any mixtures of the two; Described initiator is ammonium persulphate or Potassium Persulphate, and described solvent is the mixed solvent that water, ethanol and acetone are formed,
Step 2. is reacted the reaction system of step 1 3～24 hours at 35～75 ℃, makes thick hydrogel,
The thick hydrogel stripping and slicing that step 3. makes step 2 is fully soaked, is washed, and vacuum-drying is again pulverized, and is mixed with required hydrogel with an amount of zero(ppm) water.
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