CN103130942A - Preparation method of spherical water-absorbent resin and cold warm compress product thereof - Google Patents
Preparation method of spherical water-absorbent resin and cold warm compress product thereof Download PDFInfo
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Abstract
The invention relates to a preparation method of spherical water-absorbent resin and a cold warm compress product thereof. Especially, the invention relates to a preparation method of spherical water-absorbent resin, which comprises the following steps: step one, preparation of a water-phase solution, that is, preparing an alkali aqueous solution, then adding the aqueous solution into monomer methacrylic acid or its ester derivatives, stirring for dissolution to obtain mother liquor; adding a cross-linking agent, an initiator and an optional polymerization promoter into the mother liquor to obtain the water-phase solution; step two, preparation of an oil-phase solution, that is, adding ethyl cellulose, monoglyceride stearate, or sorbitan oleate into a solvent, uniformly stirring to obtain the oil-phase solution; step three, preparing the spherical water-absorbent resin by using a polymerization device. The spherical water-absorbent resin synthesized by the method of the invention is uniform in size, and spherical water-absorbent resins with different sizes can be obtained by adjusting the pore size and number of a screen mesh in the polymerization device; the preparation method and the device are simple; the reaction time is shortened greatly, and the yield is high.
Description
Technical field
The present invention relates to a kind of macromolecule resin preparation method, particularly, the present invention relates to a kind of preparation method and cold/hot dressing product thereof of spherical water-absorbing resin.
Background technology
Super absorbent resin (being called for short SAP) is the novel functional high molecule material of a class of the outer broad research exploitation of Present Domestic.At present, a large amount of research work has been carried out to super absorbent resin in countries in the world, has all obtained larger progress at aspects such as its kind, manufacture method, performance and Application Areass.The developed countries such as U.S., day, moral, method are on the forefront always, although the development of China SAP is started late, develop very fast.
The super absorbent resin polymerization process comprises solution method, inverse suspension method, antiphase emulsifiable method, dispersion copolymerization method and light polymerization method.Wherein solution polymerization process is simple, cost is low, but rate of polymerization is slow, and product generally must be pulverized aftertreatment, can not get regular pearl particle; The inverse suspension polymerization reaction is easy to control, and product is the small-particle pearl, and absorption speed is fast, and water-retaining capacity is high, size distribution is even, and aftertreatment is simple, only needs drying can obtain product, need not to crush and screen, but its product diameter is less, generally only has tens to the hundreds of micron.Report for large-grain bead-shaped High hydrophilous resin is few, its Literature (Zhu Xiulin, Cheng Zhenping, Lu Jianmei finishes into, polymer material science and engineering, 1998.14 (3): 12～35) reported with two step via Inverse-Phase Suspension Polymerizations, namely first synthesize the less primary particle of particle diameter with inverse suspension method, then by add this primary particle in the inverse suspension system of other new monomer, synthesized the macrobead High hydrophilous resin that particle diameter reaches 1.57mm.But this method has increased synthesis step, and making affects resin particle diameter factor and also increase, and is unfavorable for industrial production.
Summary of the invention
The invention provides a kind of preparation method of spherical water-absorbing resin, it comprises the following steps:
Step 1, the preparation of aqueous phase solution:
The aqueous solution of preparation alkali joins the aqueous solution in methacrylic acid or its ester derivative afterwards, and stirring and dissolving obtains mother liquor, and the pH value of described mother liquor is adjusted to 6.5～6.7;
Linking agent is added in described mother liquor until dissolving adds initiator and optional polymerization promotor subsequently, obtain aqueous phase solution, the density of described aqueous phase solution is 0.9～1.2g/cm
3
Step 2, the preparation of oil-phase solution:
Ethyl cellulose, glyceryl monostearate or sorbitol anhydride oleate are added to stir in solvent obtain oil-phase solution, described solvent is selected from methylcarbonate, hexanaphthene, tetracol phenixin or its combination; The add-on of described ethyl cellulose, glyceryl monostearate or sorbitol anhydride oleate is 0.1%～0.5% of described solvent total mass;
The density of described oil-phase solution is 0.8～1.0g/cm
3, and the density of described oil-phase solution is less than the density of described aqueous phase solution;
Step 3 prepares spherical water-absorbing resin:
Oil-phase solution is placed in polymerizing reactor, and this polymerizing reactor is made by the tempering transparent glass, is highly 5～6m, and diameter is 60～80mm, wherein has heating tube and plural screen cloth;
It is that 350～400nm, optical power density are under the ultraviolet source of 0.5～8w/cm that described polymerizing reactor is placed in wavelength, described aqueous phase solution is splashed in described oil-phase solution by the multilayer screen cloth granulation in described polymerizing reactor, via ultraviolet source radio polymerization cross moulding, thereby form spherical water-absorbing resin.
In one embodiment, the structure of the ester derivative of described methacrylic acid is as follows:
Wherein, R
1Be C
1-5Alkyl.
In one embodiment, in the aqueous solution of described alkali, the consumption of water is 10%～55% of aqueous phase solution total mass; Described alkali is NaOH or KOH, and its consumption is 5%～25% of aqueous phase solution total mass.
In one embodiment, the consumption of described methacrylic acid or its ester derivative is 5%～25% of aqueous phase solution total mass.
In one embodiment, described linking agent is N,N methylene bis acrylamide or divinylbenzene, and its consumption is 0.1%～0.3% of aqueous phase solution total mass.
In one embodiment, described initiator is Potassium Persulphate/sodium bisulfite or ammonium persulphate/sodium bisulfite/hydrogen peroxide, and its consumption is 0.01%～0.1% of aqueous phase solution total mass.
In one embodiment, described polymerization promotor is di-methylcarbinol amine or trolamine, and its consumption is 0.005%～0.01% of aqueous phase solution total mass.
In one embodiment, have 3 screen clothes in described polymerization reactor, the aperture of described screen cloth is followed successively by 0.8～3mm, 0.2～2.8mm, 0.05～2.6mm.Preferably, the aperture of described screen cloth is followed successively by 2mm, 1mm and 0.5mm.
The present invention also provides the prepared spherical water-absorbing resin by the preparation method of spherical water-absorbing resin of the present invention.
In addition, the present invention also provides the cold/hot dressing packing bag that utilizes spherical water-absorbing resin of the present invention to make.
The present invention has following beneficial effect: adopt the synthetic spherical water-absorbing resin size homogeneous of the inventive method, diameter is 0.2～4mm, the spherical water-absorbing resin that the aperture by adjusting screen cloth and the plus-minus screen cloth number of plies can obtain different size; The water-absorbing resin of method of the present invention preparation is spherical, and the preparation method is simple, and equipment is simple, the reaction times significantly shortens, and output is high; Utilize the cold/hot dressing packing bag of the spherical water-absorbing resin preparation of method preparation of the present invention to have the excellent cold performance of thermal protection storage, and through after Reusability, the cold/hot dressing packing bag still have higher elasticity, and spherical water-absorbing resin is non-friable.
Description of drawings
Fig. 1 is cold/hot dressing packing bag temperature temporal evolution trend map under thermal performance test;
Fig. 2 is cold/hot dressing packing bag temperature temporal evolution trend map under cold performance test.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described.Should be understood that following examples are only for explanation the present invention but not for limiting the scope of the invention.
Embodiment 1
The preparation method of the spherical water-absorbing resin of the present embodiment comprises the steps:
Step 1, the preparation of aqueous phase solution:
The NaOH of 13.2g is joined in the water of 29.2g, and stirring makes it dissolve cooling fully, after NaOH solution drops to room temperature, this solution is joined in the methacrylic acid monomer of 22.2g, and stir, cooling, to be cooled to below 25 ℃, regulating pH is 6.5～6.7;
Add again linking agent N, N-methylene-bisacrylamide 0.1～0.2g, rapid stirring, until dissolving fully, then under the situation of rapid stirring, add successively 0.08～0.1g Potassium Persulphate, the trolamine of 0.004～0.006g sodium bisulfite and 0.01g, keep system temperature 10 ℃ of left and right, obtain aqueous phase solution; The density of described aqueous phase solution is 0.9g/cm
3
Step 2, the preparation of oil-phase solution:
Take 250g glyceryl monostearate, 150kg methylcarbonate, 100kg hexanaphthene premix even, get oil-phase solution; The density of (there is no need explanation, because can directly calculate) described oil-phase solution is 0.8g/cm
3
Step 3 prepares spherical water-absorbing resin:
Oil-phase solution is placed in polymerizing reactor, described polymerizing reactor is placed under ultraviolet source, the wavelength of described ultraviolet source is 365nm, optical power density is 4w/cm, described aqueous phase solution is splashed in described oil-phase solution by the multilayer screen cloth granulation in polymerizing reactor, adopt ultraviolet source radio polymerization cross moulding, obtain spherical water-absorbing resin;
Described polymerizing reactor heating pipe built-in is highly 6m, and diameter is 60mm, has three layers of screen cloth, and screen cloth aperture from top to bottom is respectively 2mm, 1mm, 0.5mm.
The complete rear discharging of polymerization; With valve open, bead-shaped water absorbing resin is put into whizzer oil is filtered dry,, product is put into dried by the fire 5 hours at 60 ℃ of temperature of baking oven and sieve the resin washes clean with No. 2 light machine oils, obtaining product cut size is the spherical water-absorbing resin of 1.5mm.
Embodiment 2
The preparation method of the spherical water-absorbing resin of the present embodiment comprises the steps:
Step 1, the preparation of aqueous phase solution;
The KOH of 19.3g is joined in the water of 23.2g, and stirring makes it dissolve cooling fully, after KOH solution drops to room temperature, this solution is joined in the butyl methacrylate monomer of 29.2g, and stir, cooling, to be cooled to below 25 ℃, regulate pH within 6.5～6.7 scopes;
Add again linking agent N, N-methylene-bisacrylamide 0.1～0.2g, rapid stirring, until dissolving fully, then under the situation of rapid stirring, add successively 0.08～0.1g Potassium Persulphate, the hydrogen peroxide of 0.004～0.006g sodium bisulfite and 0.01g (massfraction is 30%) keeps system temperature 10 ℃ of left and right; The density of described aqueous phase solution is 1.0g/cm
3
Step 2, the preparation of oil-phase solution;
Take 300g ethyl cellulose, 100kg methylcarbonate, 150kg tetracol phenixin premix even, get oil-phase solution; The density of described oil-phase solution is 0.9g/cm
3
Step 3 prepares spherical water-absorbing resin;
Oil-phase solution is placed in polymerizing reactor, described polymerizing reactor is placed under ultraviolet source, the wavelength of described ultraviolet source is 350nm, optical power density is 0.5w/cm, described aqueous phase solution is splashed in described oil-phase solution by the multilayer screen cloth granulation in polymerizing reactor, adopt ultraviolet source radio polymerization cross moulding, obtain spherical water-absorbing resin;
Described polymerizing reactor heating pipe built-in is highly 5m, and diameter is 70mm, has three layers of screen cloth, and screen cloth aperture from top to bottom is respectively 2.5mm, 1.5mm, 1mm;
The complete rear discharging of polymerization; With valve open, bead-shaped water absorbing resin is put into whizzer oil is filtered dry,, product is put into dried by the fire 5 hours at 60 ℃ of temperature of baking oven and sieve the resin washes clean with No. 0 diesel oil, obtaining product cut size is the spherical water-absorbing resin of 2mm.
Embodiment 3
The preparation method of the spherical water-absorbing resin of the present embodiment comprises the steps:
Step 1, the preparation of aqueous phase solution;
The NaOH of 21.5g is joined in the water of 26.2g, and stirring makes it dissolve cooling fully, after NaOH solution drops to room temperature, this solution is joined in the methacrylic acid monomer of 30.2g, and stir, cooling, to be cooled to below 25 ℃, regulate pH within 6.5～6.7 scopes;
Add again linking agent N, N-methylene-bisacrylamide 0.05～0.1g, rapid stirring, until dissolving fully, then under the situation of rapid stirring, add successively 0.08～0.1g Potassium Persulphate, the di-methylcarbinol amine of 0.004～0.006g sodium bisulfite and 0.01g keeps system temperature 10 ℃ of left and right; The density of described aqueous phase solution is 1.0g/cm
3
Step 2, the preparation of oil-phase solution;
Take the 500g sorbitol anhydride oleate, 300kg methylcarbonate premix is even, gets oil-phase solution; The density of described oil-phase solution is 0.8g/cm
3
Step 3 prepares spherical water-absorbing resin;
Oil-phase solution is placed in polymerizing reactor, described polymerizing reactor is placed under ultraviolet source, the wavelength of described ultraviolet source is 400nm, optical power density is 8w/cm, described aqueous phase solution is splashed in described oil-phase solution by the multilayer screen cloth granulation in polymerizing reactor, adopt ultraviolet source radio polymerization cross moulding, obtain spherical water-absorbing resin;
Described polymerizing reactor heating pipe built-in is highly 5m, and diameter is 70mm, has three layers of screen cloth, and screen cloth aperture from top to bottom is respectively 3mm, 2.5mm, 1.5mm;
Described aqueous phase solution is splashed in described oil-phase solution, adopt ultraviolet source radio polymerization cross moulding, obtain spherical water-absorbing resin;
The complete rear discharging of polymerization; With valve open, bead-shaped water absorbing resin is put into whizzer oil is filtered dry,, product is put into dried by the fire 4.8 hours at 65 ℃ of temperature of baking oven and sieve the resin washes clean with No. 0 diesel oil, getting product cut size is the spherical water-absorbing resin of 2.5mm.
The preparation method of the spherical water-absorbing resin of the present embodiment comprises the steps:
Step 1, the preparation of aqueous phase solution;
The NaOH of 13.2g is joined in the water of 29.2g, and stirring makes it dissolve cooling fully, after NaOH solution drops to room temperature, this solution is joined in the methacrylic acid monomer of 10.2g, and stir, cooling, to be cooled to below 25 ℃, regulate pH within 6.5～6.7 scopes;
Add again linking agent divinylbenzene 0.05～0.1g, rapid stirring, until dissolving fully, then under the situation of rapid stirring, add successively 0.06～0.08g Potassium Persulphate, 0.003 the hydrogen peroxide of～0.005g sodium bisulfite and 0.01g (massfraction is 30%) keeps system temperature 10 ℃ of left and right; The density of described aqueous phase solution is 1.2g/cm
3
Step 2, the preparation of oil-phase solution;
Take 1250g ethyl cellulose, 150kg methylcarbonate, 100kg hexanaphthene premix even, get oil-phase solution; The density of described oil-phase solution is 1.0g/cm
3
Step 3 prepares spherical water-absorbing resin;
Oil-phase solution is placed in polymerizing reactor, described polymerizing reactor is placed under ultraviolet source, the wavelength of described ultraviolet source is 385nm, optical power density is 6w/cm, described aqueous phase solution is splashed in described oil-phase solution by the multilayer screen cloth granulation in polymerizing reactor, adopt ultraviolet source radio polymerization cross moulding, obtain spherical water-absorbing resin;
Described polymerizing reactor heating pipe built-in is highly 6m, and diameter is 60mm, has three layers of screen cloth, and screen cloth aperture from top to bottom is respectively 1mm, 0.5mm, 0.2mm;
The complete rear discharging of polymerization; With valve open, bead-shaped water absorbing resin is put into whizzer oil is filtered dry,, product is put into dried by the fire 4.5 hours at 70 ℃ of temperature of baking oven and sieve the resin washes clean with No. 0 diesel oil, getting product cut size is the spherical water-absorbing resin of 0.5mm.
The preparation method of the spherical water-absorbing resin of the present embodiment comprises the steps:
Step 1, the preparation of aqueous phase solution;
The NaOH of 25.2g is joined in the water of 29.2g, and stirring makes it dissolve cooling fully, after NaOH solution drops to room temperature, this solution is joined in the methacrylic acid monomer of 35.2g, and stir, cooling, to be cooled to below 25 ℃, regulate pH within 6.5～6.7 scopes;
Add again linking agent N,N methylene bis acrylamide 0.1～0.2g, rapid stirring, until then dissolving fully under the situation of rapid stirring, adds 0.1～0.12g Potassium Persulphate successively, 0.004 the di-methylcarbinol amine of～0.006g sodium bisulfite and 0.01g keeps system temperature 10 ℃ of left and right; The density of described aqueous phase solution is 0.9g/cm
3
Step 2, the preparation of oil-phase solution;
Take the 1kg glyceryl monostearate, 300kg methylcarbonate premix is even, gets oil-phase solution; The density of described oil-phase solution is 0.8g/cm
3
Step 3 prepares spherical water-absorbing resin;
Oil-phase solution is placed in polymerizing reactor, described polymerizing reactor is placed under ultraviolet source, the wavelength of described ultraviolet source is 400nm, optical power density is 8w/cm, described aqueous phase solution is splashed in described oil-phase solution by the multilayer screen cloth granulation in polymerizing reactor, adopt ultraviolet source radio polymerization cross moulding, obtain spherical water-absorbing resin;
Described polymerizing reactor heating pipe built-in is highly 6m, and diameter is 60mm, has three layers of screen cloth, and screen cloth aperture from top to bottom is respectively 0.8mm, 0.2mm, 0.05mm;
The complete rear discharging of polymerization; With valve open, bead-shaped water absorbing resin is put into whizzer oil is filtered dry,, product is put into dried by the fire 4 hours at 80 ℃ of temperature of baking oven and sieve the resin washes clean with No. 0 diesel oil, getting product cut size is the spherical water-absorbing resin of 0.2mm.
The preparation method of the spherical water-absorbing resin of the present embodiment comprises the steps:
Step 1, the preparation of aqueous phase solution;
The NaOH of 28.2g is joined in the water of 29.2g, and stirring makes it dissolve cooling fully, after NaOH solution drops to room temperature, this solution is joined in the methacrylic acid monomer of 32.2g, and stir, cooling, to be cooled to below 25 ℃, regulate pH within 6.5～6.7 scopes;
Add again linking agent N,N methylene bis acrylamide 0.1～0.2g, rapid stirring, until then dissolving fully under the situation of rapid stirring, adds 0.08～0.1g Potassium Persulphate successively, 0.004 the di-methylcarbinol amine of～0.006g sodium bisulfite and 0.01g keeps system temperature 10 ℃ of left and right; The density of described aqueous phase solution is 1.0g/cm
3
Step 2, the preparation of oil-phase solution;
Take the 300g glyceryl monostearate, 300kg hexanaphthene premix is even, gets oil-phase solution; The density of described oil-phase solution is 0.8g/cm
3
Step 3 prepares spherical water-absorbing resin;
Oil-phase solution is placed in polymerizing reactor, described polymerizing reactor is placed under ultraviolet source, the wavelength of described ultraviolet source is 365nm, optical power density is 2w/cm, described aqueous phase solution is splashed in described oil-phase solution by the multilayer screen cloth granulation in polymerizing reactor, adopt ultraviolet source radio polymerization cross moulding, obtain spherical water-absorbing resin;
Described polymerizing reactor heating pipe built-in is highly 5m, and diameter is 70mm, has three layers of screen cloth, and screen cloth aperture from top to bottom is respectively 3mm, 3mm, 2.5mm;
The complete rear discharging of polymerization; With valve open, bead-shaped water absorbing resin is put into whizzer oil is filtered dry,, product is put at 60 ℃ of temperature of baking oven dried and sieve the resin washes clean with No. 0 diesel oil, getting product cut size is the spherical water-absorbing resin of 4mm.
Embodiment 7
The preparation method of the spherical water-absorbing resin of the present embodiment comprises the steps:
Step 1, the preparation of aqueous phase solution;
The NaOH of 10.2g is joined in the water of 29.2g, and stirring makes it dissolve cooling fully, after NaOH solution drops to room temperature, this solution is joined in the methacrylic acid monomer of 22.2g, and stir, cooling, to be cooled to below 25 ℃, regulate pH within 6.5～6.7 scopes;
Add again linking agent N, N-methylene-bisacrylamide 0.05～0.1g, rapid stirring, until dissolving fully, then under the situation of rapid stirring, add successively 0.06～0.08g Potassium Persulphate, the di-methylcarbinol amine of 0.004～0.006g sodium bisulfite and 0.01g keeps system temperature 10 ℃ of left and right; The density of described aqueous phase solution is 1.2g/cm
3
Step 2, the preparation of oil-phase solution;
Take 400g glyceryl monostearate, 150kg hexanaphthene, 100kg tetracol phenixin premix even, get oil-phase solution; The density of described oil-phase solution is 1.0g/cm
3
Step 3 prepares spherical water-absorbing resin;
Oil-phase solution is placed in polymerizing reactor, described polymerizing reactor is placed under ultraviolet source, the wavelength of described ultraviolet source is 400nm, optical power density is 4w/cm, described aqueous phase solution is splashed in described oil-phase solution by the multilayer screen cloth granulation in polymerizing reactor, adopt ultraviolet source radio polymerization cross moulding, obtain spherical water-absorbing resin;
Described polymerizing reactor heating pipe built-in is highly 6m, and diameter is 70mm, has three layers of screen cloth, and screen cloth aperture from top to bottom is respectively 2mm, 1mm, 0.5mm;
The complete rear discharging of polymerization; With valve open, bead-shaped water absorbing resin is put into whizzer oil is filtered dry,, product is put at 60 ℃ of temperature of baking oven dried and sieve the resin washes clean with No. 0 diesel oil, getting product cut size is the spherical water-absorbing resin of 1mm.
The preparation method of the spherical water-absorbing resin of the present embodiment comprises the steps:
Step 1, the preparation of aqueous phase solution;
The NaOH of 18.2g is joined in the water of 25.2g, and stirring makes it dissolve cooling fully, after NaOH solution drops to room temperature, this solution is joined in the methacrylic acid monomer of 12.2g, and stir, cooling, to be cooled to below 25 ℃, regulate pH within 6.5～6.7 scopes;
Add again linking agent N, N-methylene-bisacrylamide 0.1～0.2g, rapid stirring, until dissolving fully, then under the situation of rapid stirring, add successively 0.08～0.1g Potassium Persulphate, the hydrogen peroxide of 0.004～0.006g sodium bisulfite and 0.01g (massfraction is 30%) keeps system temperature 10 ℃ of left and right; The density of described aqueous phase solution is 1.1g/cm
3
Step 2, the preparation of oil-phase solution;
Take the 800g sorbitol anhydride oleate, 300kg methylcarbonate premix is even, gets oil-phase solution; The density of described oil-phase solution is 1.0g/cm
3
Step 3 prepares spherical water-absorbing resin;
Oil-phase solution is placed in polymerizing reactor, described polymerizing reactor is placed under ultraviolet source, the wavelength of described ultraviolet source is 365nm, optical power density is 1w/cm, described aqueous phase solution is splashed in described oil-phase solution by the multilayer screen cloth granulation in polymerizing reactor, adopt ultraviolet source radio polymerization cross moulding, obtain spherical water-absorbing resin;
Described polymerizing reactor heating pipe built-in is highly 6m, and diameter is 80mm, has three layers of screen cloth, and screen cloth aperture from top to bottom is respectively 3mm, 2mm, 1mm;
The complete rear discharging of polymerization; With valve open, bead-shaped water absorbing resin is put into whizzer oil is filtered dry,, product is put at 60 ℃ of temperature of baking oven dried and sieve the resin washes clean with No. 0 diesel oil, getting product cut size is the spherical water-absorbing resin of 1.5mm.
The preparation method of the spherical water-absorbing resin of the present embodiment comprises the steps:
Step 1, the preparation of aqueous phase solution;
The NaOH of 8.2g is joined in the water of 29.2g, and stirring makes it dissolve cooling fully, after NaOH solution drops to room temperature, this solution is joined in the methacrylic acid monomer of 12.2g, and stir, cooling, to be cooled to below 25 ℃, regulate pH within 6.5～6.7 scopes;
Add again linking agent N,N methylene bis acrylamide 0.1～0.2g, rapid stirring, until then dissolving fully under the situation of rapid stirring, adds 0.08～0.1g Potassium Persulphate successively, 0.004 the di-methylcarbinol amine of～0.006g sodium bisulfite and 0.01g keeps system temperature 10 ℃ of left and right; The density of described aqueous phase solution is 0.9g/cm
3
Step 2, the preparation of oil-phase solution;
Take 1.2kg glyceryl monostearate, 150kg methylcarbonate, 100kg hexanaphthene premix even, get oil-phase solution; The density of described oil-phase solution is 0.8g/cm
3
Step 3 prepares spherical water-absorbing resin;
Oil-phase solution is placed in polymerizing reactor, described polymerizing reactor is placed under ultraviolet source, the wavelength of described ultraviolet source is 365nm, optical power density is 5w/cm, described aqueous phase solution is splashed in described oil-phase solution by the multilayer screen cloth granulation in polymerizing reactor, adopt ultraviolet source radio polymerization granulation cross moulding, obtain spherical water-absorbing resin;
Described polymerizing reactor heating pipe built-in is highly 5m, and diameter is 70mm, has three layers of screen cloth, and screen cloth aperture from top to bottom is respectively 2mm, 2mm, 1.2mm;
The complete rear discharging of polymerization; With valve open, bead-shaped water absorbing resin is put into whizzer oil is filtered dry,, product is put at 60 ℃ of temperature of baking oven dried and sieve the resin washes clean with No. 0 diesel oil, getting product cut size is the spherical water-absorbing resin of 1.8mm.
The preparation method of the spherical water-absorbing resin of the present embodiment comprises the steps:
Step 1, the preparation of aqueous phase solution;
The NaOH of 28.2g is joined in the water of 29.2g, and stirring makes it dissolve cooling fully, after NaOH solution drops to room temperature, this solution is joined in the methacrylic acid monomer of 32.2g, and stir, cooling, to be cooled to below 25 ℃, regulate pH within 6.5～6.7 scopes;
Add again linking agent N,N methylene bis acrylamide 0.1～0.2g, rapid stirring, until then dissolving fully under the situation of rapid stirring, adds 0.08～0.1g Potassium Persulphate successively, 0.004 the di-methylcarbinol amine of～0.006g sodium bisulfite and 0.01g keeps system temperature 10 ℃ of left and right; The density of described aqueous phase solution is 1.0g/cm
3
Step 2, the preparation of oil-phase solution;
Take 1.2kg ethyl cellulose, 150kg hexanaphthene, 100kg tetracol phenixin premix even, get oil-phase solution; The density of described oil-phase solution is 0.9g/cm
3
Step 3 prepares spherical water-absorbing resin;
Oil-phase solution is placed in polymerizing reactor, described polymerizing reactor is placed under ultraviolet source, the wavelength of described ultraviolet source is 400nm, optical power density is 6w/cm, described aqueous phase solution is splashed in described oil-phase solution by the multilayer screen cloth granulation in polymerizing reactor, adopt ultraviolet source radio polymerization cross moulding, obtain spherical water-absorbing resin;
Described polymerizing reactor heating pipe built-in is highly 5.5m, and diameter is 80mm, has three layers of screen cloth, and screen cloth aperture from top to bottom is respectively 3mm, 2.8mm, 2.6mm;
The complete rear discharging of polymerization; With valve open, bead-shaped water absorbing resin is put into whizzer oil is filtered dry,, product is put at 60 ℃ of temperature of baking oven dried and sieve the resin washes clean with No. 0 diesel oil, getting product cut size is the spherical water-absorbing resin of 3.2mm.
Embodiment 11
Utilize the spherical water-absorbing resin of previous embodiment preparation to prepare the cold/hot dressing packing bag, obtained extraordinary effect.
The cold/hot dressing packing bag as a kind of easily, important physiotherapy product is widely used in medical treatment, the packing bag that uses at present mostly is the pliable-closure packing that stores water, the risk of seepage is arranged, and use inconvenience, the cold and hot property retention time is not long.And utilize the spherical water-absorbing resin of the inventive method preparation to can be made into the cold/hot dressing packing bag, glittering and translucent as spherical water-absorbing resin suction foaming after image crystal, elasticity is splendid, transparency is high, solved the break risk of rear leakage of outer packaging, and morphological appearance, the cold and hot property retention time is longer, low temperature does not freeze, and keeps elasticity.Refrigerating fulid and spherical water-absorbing resin are mixed in proportion, and after refrigerating fulid was sucked, soft packaging bag was advanced in can, formed the different spherical water-absorbing resin cold/hot dressing product of size.
11.1 the preparation method of cold/hot dressing packing bag
The spherical water-absorbing resin that utilizes previous embodiment to prepare prepares the method for cold/hot dressing packing bag, comprises the steps:
The first step, polyvalent alcohol, sterilizing agent is soluble in water, stir it is mixed, get mixing solutions;
Described polyvalent alcohol is propylene glycol, glycerol, tetramethylolmethane or high fatty alcohol analog derivative;
Described sterilizing agent is thiazoline ketone or derivatives thereof;
Second step is mixed in proportion spherical water-absorbing resin and mixing solutions, waits for that 2～3h gets final product the abundant imbibition of resin;
In the 3rd step, the resin that second step is obtained is circulated in outer packaging, drained unnecessary gas, and the high frequency sealing namely gets spherical water-absorbing resin cold/hot dressing packing bag finished product; Outer packaging is the soft material sealed package, and material is the asepsis environment-protecting materials such as PVC, TPU, EVA, PU.
Content in the cold/hot dressing packing bag of preparation, the resin balls size homogeneous after namely expanding, diameter is 5～15mm, has excellent cold insulation thermal protection performance, and still guarantee pliability and elasticity in the low temperature environment of-20 ℃.
Table 1 preparation cold/hot dressing packing bag
11.2 the cold and hot performance test of spherical water-absorbing resin cold/hot dressing packing bag
Choosing the cold/hot dressing packing bag of sequence number 1 method preparation in 11.1 tests;
Pretreatment mode: thermal characteristics: product is heated 30s in the microwave oven of 800w; Cold performance: with product freezing 2.5h in the environment of-20 ℃; The envrionment temperature of test: 25 ℃.20 groups of circulations have been carried out in test altogether, and table 2 is the thermal performance test data, and table 3 is cold performance test data; Fig. 1 is cold/hot dressing packing bag temperature temporal evolution trend map under thermal performance test, and Fig. 2 is cold/hot dressing packing bag temperature temporal evolution trend map under cold performance test.Can find out from data and figure, after pre-treatment, in the envrionment temperature of 25 ℃, after 1h, spherical water-absorbing resin cold/hot dressing packing bag has still embodied the excellent cold performance of thermal protection storage; And through the cold and hot performance test of 20 groups of circulations, spherical water-absorbing resin cold/hot dressing packing bag still has higher elasticity, and non-friable.
Table 2 thermal performance test data
| Time/min | Temperature/℃ | Time/min | Temperature/℃ |
| 1 | 47 | 31 | 39.3 |
| 2 | 46.6 | 32 | 39.2 |
| 3 | 46.3 | 33 | 38.9 |
| 4 | 46.2 | 34 | 38.6 |
| 5 | 45.9 | 35 | 38.3 |
| 6 | 45.6 | 36 | 38.1 |
| 7 | 45.4 | 37 | 37.9 |
| 8 | 45.2 | 38 | 37.7 |
| 9 | 45 | 39 | 37.6 |
| 10 | 44.8 | 40 | 37.5 |
| 11 | 44.6 | 41 | 37.4 |
| 12 | 44.4 | 42 | 37.2 |
| 13 | 44.2 | 43 | 37 |
| 14 | 44 | 44 | 36.9 |
| 15 | 43.7 | 45 | 36.6 |
| 16 | 43.5 | 46 | 36.1 |
| 17 | 43.3 | 47 | 35.8 |
| 18 | 43 | 48 | 35.5 |
| 19 | 42.8 | 49 | 35.4 |
| 20 | 42.6 | 50 | 35.2 |
| 21 | 42.3 | 51 | 35 |
| 22 | 42 | 52 | 34.9 |
| 23 | 41.8 | 53 | 34.8 |
| 24 | 41.5 | 54 | 34.6 |
| 25 | 41.3 | 55 | 34.3 |
| 26 | 41 | 56 | 34.2 |
| 27 | 40.6 | 57 | 34.1 |
| 28 | 40.2 | 58 | 33.9 |
| 29 | 39.8 | 59 | 33.9 |
| 30 | 39.5 | 60 | 33.7 |
The cold performance test data of table 3
| Time/min | Temperature/℃ | Time/min | Temperature/℃ |
| 1 | -9.2 | 31 | -7.1 |
| 2 | -9.3 | 32 | -7 |
| 3 | -9.2 | 33 | -6.9 |
| 4 | -9.2 | 34 | -6.9 |
| 5 | -9.1 | 35 | -6.8 |
| 6 | -9 | 36 | -6.7 |
| 7 | -9 | 37 | -6.5 |
| 8 | -9 | 38 | -6.4 |
| 9 | -9 | 39 | -6.3 |
| 10 | -8.9 | 40 | -6.2 |
| 11 | -8.9 | 41 | -6.1 |
| 12 | -8.8 | 42 | -6 |
| 13 | -8.8 | 43 | -6 |
| 14 | -8.7 | 44 | -5.9 |
| 15 | -8.6 | 45 | -5.8 |
| 16 | -8.5 | 46 | -5.7 |
| 17 | -8.4 | 47 | -5.7 |
| 18 | -8.3 | 48 | -5.5 |
| 19 | -8.1 | 49 | -5.5 |
| 20 | -8 | 50 | -5.3 |
| 21 | -7.9 | 51 | -5.2 |
| 22 | -7.9 | 52 | -5.1 |
| 23 | -7.8 | 53 | -5 |
| 24 | -7.7 | 54 | -4.9 |
| 25 | -7.6 | 55 | -4.8 |
| 26 | -7.5 | 56 | -4.7 |
| 27 | -7.5 | 57 | -4.6 |
| 28 | -7.3 | 58 | -4.5 |
| 29 | -7.2 | 59 | -4.3 |
| 30 | -7.2 | 60 | -4.2 |
Claims (11)
1. the preparation method of a spherical water-absorbing resin, is characterized in that, described preparation method comprises the following steps:
Step 1, the preparation of aqueous phase solution:
The aqueous solution of preparation alkali joins the aqueous solution in methacrylic acid or its ester derivative afterwards, and stirring and dissolving obtains mother liquor, and the pH value of described mother liquor is adjusted to 6.5～6.7;
Linking agent is added in described mother liquor until dissolving adds initiator and optional polymerization promotor subsequently, obtain aqueous phase solution, the density of described aqueous phase solution is 0.9～1.2g/cm
3
Step 2, the preparation of oil-phase solution:
Ethyl cellulose, glyceryl monostearate or sorbitol anhydride oleate are added to stir in solvent obtain oil-phase solution, described solvent is selected from methylcarbonate, hexanaphthene, tetracol phenixin or its combination; The add-on of described ethyl cellulose, glyceryl monostearate or sorbitol anhydride oleate is 0.1%～0.5% of described solvent total mass;
The density of described oil-phase solution is 0.8～1.0g/cm
3, and the density of described oil-phase solution is less than the density of described aqueous phase solution;
Step 3 prepares spherical water-absorbing resin:
Oil-phase solution is placed in polymerizing reactor, and this polymerizing reactor is made by the tempering transparent glass, is highly 5～6m, and diameter is 60～80mm, wherein has heating tube and plural screen cloth;
It is that 350～400nm, optical power density are under the ultraviolet source of 0.5～8w/cm that described polymerizing reactor is placed in wavelength, described aqueous phase solution is splashed in described oil-phase solution by the multilayer screen cloth granulation in described polymerizing reactor, via ultraviolet source radio polymerization cross moulding, thereby form spherical water-absorbing resin.
2. the preparation method of spherical water-absorbing resin according to claim 1, is characterized in that, the structure of the ester derivative of described methacrylic acid is as follows:
Wherein, R
1Be C
1-5Alkyl.
3. the preparation method of spherical water-absorbing resin according to claim 1, is characterized in that, the consumption of the water in the aqueous solution of described alkali is 10%～55% of aqueous phase solution total mass; Described alkali is NaOH or KOH, and its consumption is 5%～25% of aqueous phase solution total mass.
4. the preparation method of spherical water-absorbing resin according to claim 1, is characterized in that, the consumption of described methacrylic acid or its ester derivative is 5%～25% of aqueous phase solution total mass.
5. the preparation method of spherical water-absorbing resin according to claim 1, is characterized in that, described linking agent is N,N methylene bis acrylamide or divinylbenzene, and its consumption is 0.1%～0.3% of aqueous phase solution total mass.
6. the preparation method of spherical water-absorbing resin according to claim 1, is characterized in that, described initiator is Potassium Persulphate/sodium bisulfite or ammonium persulphate/sodium bisulfite/hydrogen peroxide, and its consumption is 0.01%～0.1% of aqueous phase solution total mass.
7. the preparation method of spherical water-absorbing resin according to claim 1, is characterized in that, described polymerization promotor is di-methylcarbinol amine or trolamine, and its consumption is 0.005%～0.01% of aqueous phase solution total mass.
8. the preparation method of spherical water-absorbing resin according to claim 1, is characterized in that, has 3 screen clothes in described polymerization reactor, and the aperture of described screen cloth is followed successively by 0.8～3mm, 0.2～2.8mm and 0.05～2.6mm.
9. the preparation method of spherical water-absorbing resin according to claim 8, the aperture of wherein said screen cloth is followed successively by 2mm, 1mm and 0.5mm.
10. spherical water-absorbing resin that is made by the preparation method of the described spherical water-absorbing resin of claim 1-9 any one.
11. cold/hot dressing packing bag that utilizes spherical water-absorbing resin as claimed in claim 10 to make.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103408689A (en) * | 2013-08-14 | 2013-11-27 | 武汉工程大学 | Synthetic method for instant-absorption type super absorbent resin |
| CN107647962A (en) * | 2017-09-30 | 2018-02-02 | 浙江三赢新材料有限公司 | Cold and hot compress product with temperature warning function |
| CN107880284A (en) * | 2016-09-30 | 2018-04-06 | 天津世济生物工程有限公司 | A kind of preparation method of cold-resistant, heat-resisting Super Absorbent Polymer Particles |
| CN109694441A (en) * | 2017-10-20 | 2019-04-30 | 中蓝晨光化工研究设计院有限公司 | A kind of pearl high hydroscopic resin and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1786040A (en) * | 2005-11-11 | 2006-06-14 | 湖南省原子能农业应用研究所 | Preparation method of spherical water absorption resin |
| CN101481434A (en) * | 2009-01-22 | 2009-07-15 | 潍坊中石科技有限公司 | Method for preparing big particle pearl-like water absorption resin, resin prepared thereby and preparing apparatus |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1786040A (en) * | 2005-11-11 | 2006-06-14 | 湖南省原子能农业应用研究所 | Preparation method of spherical water absorption resin |
| CN101481434A (en) * | 2009-01-22 | 2009-07-15 | 潍坊中石科技有限公司 | Method for preparing big particle pearl-like water absorption resin, resin prepared thereby and preparing apparatus |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103408689A (en) * | 2013-08-14 | 2013-11-27 | 武汉工程大学 | Synthetic method for instant-absorption type super absorbent resin |
| CN103408689B (en) * | 2013-08-14 | 2016-03-02 | 武汉工程大学 | A kind of synthetic method of wink suction type High hydrophilous resin |
| CN107880284A (en) * | 2016-09-30 | 2018-04-06 | 天津世济生物工程有限公司 | A kind of preparation method of cold-resistant, heat-resisting Super Absorbent Polymer Particles |
| CN107647962A (en) * | 2017-09-30 | 2018-02-02 | 浙江三赢新材料有限公司 | Cold and hot compress product with temperature warning function |
| CN107647962B (en) * | 2017-09-30 | 2022-05-13 | 浙江三赢新材料有限公司 | Cold and hot compress product with temperature warning function |
| CN109694441A (en) * | 2017-10-20 | 2019-04-30 | 中蓝晨光化工研究设计院有限公司 | A kind of pearl high hydroscopic resin and preparation method thereof |
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