CN109161145A - A kind of degradable high-elastic sponge - Google Patents
A kind of degradable high-elastic sponge Download PDFInfo
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- CN109161145A CN109161145A CN201810947983.8A CN201810947983A CN109161145A CN 109161145 A CN109161145 A CN 109161145A CN 201810947983 A CN201810947983 A CN 201810947983A CN 109161145 A CN109161145 A CN 109161145A
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/30—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by mixing gases into liquid compositions or plastisols, e.g. frothing with air
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C08J9/0028—Use of organic additives containing nitrogen
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- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
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- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
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Abstract
The present invention relates to sponge fields, more particularly to a kind of degradable high-elastic sponge that is environmental-friendly and having excellent mechanical property, the degradable high-elastic sponge prepares the substance that raw material includes following parts by weight: 100 parts of composite sponge matrix, 3~5.5 parts by weight of A additive, 4~9 parts by weight of B additive, 0.5~1.1 parts by weight of zinc oxide, 1.75~2.55 parts by weight of prodan, 1.1~2.35 parts by weight of 2.35~4.5 parts by weight of A promotor and B promotor.The matrix used material of the present invention and wherein a large amount of components are green environmental protection degradable material, obtained product is also more environmentally protective, with good biocompatibility, preparation process and use process are non-hazardous to human body, and also there is good chemical stability and outstanding mechanical property, it is extremely outstanding especially on elastic property.
Description
Technical field
The present invention relates to sponge fields, more particularly to one kind is environmental-friendly and has the degradable high-elastic of excellent mechanical property
Sponge.
Background technique
Sponge is a kind of extremely common porous material, has good water imbibition, partially has good elasticity, deformation
Restorative etc. performance can be used in clean article or the seat cushion for producing some comfortable softnesses.
The common sponge of people is made of wood cellulose fibers or foamed plastic polymer.In addition, also having by spongia
Manufactured natural sponge, most of natural sponges are used for clean body or drawing.In addition, there are also close made of three classes other materials
At sponge, respectively low-density polyethers (not water-absorbing sponge), polyvinyl alcohol (high-absorbent material, without obvious stomata) and polyester.
For at present, the manufacturing cost of sponge is positively correlated with sponge density in the market, and density is higher, and cost is also higher, but
The physical property of low-density sponge is often not so good as high-density sponge, especially as in terms of use, thus seek
A kind of low-density of mechanical property standard needed for low-density but has excellent mechanical performances that can meet seat cushion sponge in the world is high-elastic
Property sponge is a great development direction.The pollution produced during the preparation process of sponge is larger at present simultaneously, and sponge is mostly artificial high poly-
Object is difficult to degrade, and foaming agent causes damages to people in foaming process, pollute the environment and one urgently to be resolved is asked
Topic.
Patent Office of the People's Republic of China disclosed the hair of an a kind of low-density high-mechanic sponge and manufacture craft on 2 15th, 2017
Bright patent application document, application publication number CN106397711A, the patent of invention pass through the expansion density for reducing sponge, so that
Required production material is greatly decreased when producing the sponge of same volume, reduces production cost, has on the other hand selected polyethers
Polyalcohol and polymer polyatomic alcohol improve the hardness of sponge, avoid and cause asking for physical property decline because density is too low
Topic.But it there are still the pollution produced during the preparation process of sponge is larger, artificial high polymer is difficult to degrade, and foaming agent was foaming
The problem of causing damages, polluting the environment to people in journey.
Summary of the invention
Excessively high to solve above-specified high density sponge production cost, low-density sponge mechanical property is poor can not to meet seat cushion sea
Continuous standard, and the pollution produced during the preparation process of current sponge is larger, artificial high polymer is difficult to degrade, and foaming agent was foaming
The problem of causing damages, polluting the environment to people in journey, the present invention provides a kind of environmental-friendly and have excellent mechanics
The degradable high-elastic sponge of performance.
To achieve the above object, the invention adopts the following technical scheme:
A kind of degradable high-elastic sponge, the degradable high-elastic sponge prepare the substance that raw material includes following parts by weight: multiple
100 parts of sponge matrix of conjunction, 3~5.5 parts by weight of A additive, 4~9 parts by weight of B additive, 0.5~1.1 parts by weight of zinc oxide, fluorine
1.75~2.55 parts by weight of sodium metasilicate, 1.1~2.35 parts by weight of 2.35~4.5 parts by weight of A promotor and B promotor.
Preferably, the degradable high-elastic sponge prepares the substance that raw material includes following parts by weight: composite sponge
100 parts of matrix, 3.95~4.25 parts by weight of A additive, 6.75~7.5 parts by weight of B additive, 0.8~1.05 weight of zinc oxide
Part, 1.95~2.15 parts by weight of prodan, 1.9~2.15 parts by weight of 3.15~3.5 parts by weight of A promotor and B promotor.
Preferably, the degradable high-elastic sponge prepares the substance that raw material includes following parts by weight: composite sponge
100 parts of matrix, 4.05 parts by weight of A additive, 7.1 parts by weight of B additive, 0.95 parts by weight of zinc oxide, 2.05 weight of prodan
Measure part, 1.95 parts by weight of 3.35 parts by weight of A promotor and B promotor.
Preferably, the preparation method of the composite sponge matrix includes following preparation step:
1) prepared by polymeric additive:
A) deionized water of maleic anhydride and its 50 times of parts by weight is mixed, is added to the instrument equipped with reflux condensate device
In, and simultaneously constant temperature is stirred to react 30~35min to 60 DEG C under the conditions of 60 DEG C by oil bath heating, revolving speed is 500~1000r/
Min, hydrolysis obtain maleic acid anhydride solution；
B) under condition of ice bath, ammonium hydroxide is added into the maleic acid anhydride solution that step a) is obtained, is warming up to after mixing evenly
85 DEG C, 175~200min is reacted, revolving speed is 500~1000r/min, imported while hot after reflection in porcelain container 80~
It is dry under the conditions of 85 DEG C, the maleic anhydride ammonium salt of white solid is obtained after dry；
C) by the maleic anhydride ammonium salt that step b) is obtained be placed in 150~230 DEG C of hot environment carry out polymerization reaction 1~
5h, polysuccinimide, and be ground to powdered；
D) powdered polysuccinimide obtained by step c) is added in excessive water, stirring and dissolving, with the hydrogen-oxygen of 0.5mol/L
Change sodium water solution adjusting pH value and hydrolyze 60~80min under 50 DEG C of water bath conditions to 10.9~11.2, and with the hydrogen of 0.5mol/L
Aqueous solution of sodium oxide keeps hydrolytic process pH value to be maintained at 10.8~11.2, then to anhydrous second is added in solution while stirring
Alcohol is slowly added dropwise after generating brown oil drop, until upper layer does not generate white opacity thing, carries out concussion liquid separation to solution, goes
Lower liquid is placed in dry in 120~130 DEG C of environment to mass change per hour and add less than 0.5% to get to macromolecule
Agent；
2) bentonite is dissolved in the deionized water of its 100~120 times of parts by weight, 60~80min of ultrasonic disperse is carried out to it, led to
Enter nitrogen and 30~35min of purging is carried out to it, makes its degassing；
3) acrylamide, polyvinyl alcohol, N, N- di-2-ethylhexylphosphine oxide are added in the bentonite aqueous dispersion to step 2) after degassed
Lauryl sodium sulfate is added after being uniformly mixed in the mixture of polymeric additive obtained by acrylamide and step 1)
Quickly 15~20min of stirring is carried out with the revolving speed of 600~800r/min with auxiliary blowing agent, then is turned with 120~180r/min
Speed carries out mixing slowly 20~30min, and ammonium persulfate is then added and starts to react, control is warming up to 75 DEG C and protects in reaction process
5~6h is held, is rinsed after reaction with deionized water, and dry 48~50h under the conditions of 45~50 DEG C, obtains composite sponge base
Body.
Composite sponge matrix is because it is a kind of nonionic list using acrylamide monomer as synthon in the present invention
Certain salt resistant character of prepared composite sponge matrix, acrylamide monomer and crosslinking agent can be improved with when each poly- in body
Hydrogel crosslinking degree can all be influenced by closing object and initiator amount, to influence its performance.The quality of crosslinking agent is smaller to be caused to hand over
It is lower to join density, it is soluble, cause its water imbibition poor；On the contrary, high quality crosslinking agent generates more crosslinking points, generate additional
Network simultaneously reduces available free volume, thus can also reduce its water imbibition.Selected N,N methylene bis acrylamide is made
For crosslinking agent have with acrylamide monomer it is best be adapted to degree, provide a fabulous crosslinking degree for hydrogel, mention
Its preferably water absorbing properties performance is supplied.If furthermore the same dosage of initiator ammonium persulfate is excessive, it will cause reactions acutely, produces
Raw a large amount of by-product simultaneously causes its structure to be destroyed, and causes performance to decline, if initiator ammonium persulfate dosage is too small, will lead to
Not exclusively, crosslinking/linear non-crosslinked network structure is unstable for reaction, will also result in performance decline.
In composite sponge matrix, crosslinking/linear non-crosslinked mixed network structure makes composite sponge matrix have pole
For excellent mechanical property, compared to common sea in the performances such as elasticity modulus, compression set value and elongation at break
Continuous body has great promotion, and generates collaboration foaming effect by lauryl sodium sulfate and auxiliary blowing agent, compared to oil
Sour potassium, ammonium sulfate, glycerol etc. easily cause pollution or generate dysgenic foaming agent, the more value of environmental protection to human body.
Preferably, mass fraction proportion raw materials used in the composite sponge matrix is 1~5 parts by weight of bentonite,
80~125 parts by weight of acrylamide monomer, 25~35 parts by weight of polyvinyl alcohol, N, N- methylene-bisacrylamide 5.5~12.5
Parts by weight, 3~5 parts by weight of ammonium persulfate, 3.5~5.5 parts by weight of lauryl sodium sulfate, 0.35~0.85 weight of auxiliary blowing agent
Measure part, 4~7 parts by weight of 3.5~6 parts by weight of maleic anhydride and ammonium hydroxide.
Preferably, the auxiliary blowing agent is sodium sulfate of polyethenoxy ether of fatty alcohol.
Lauryl sodium sulfate is a kind of anionic surfactant, belongs to surfactant-based foaming agent, can be effective
Reduce liquid surface tension simultaneously liquid film surface electric double layer arrange and surround air, formed bubble, then by single isolated bubbles into
And foam group is formed, there is extremely strong foaming capacity, and biological degradability degree can degrade greatly 90% or more in recycling
And it avoids pollution；Sodium sulfate of polyethenoxy ether of fatty alcohol also known as be ethoxylated alkyl sulfate, fatty alcohol-ether sodium sulfate, equally
It is a kind of anionic surfactant, it is very mild to human body and at 50 DEG C or more or i.e. decomposable under mildly acidic conditions,
It hydrolyzes, generates nuisanceless substance, thus can also dramatically avoid pollution environment in recycling, and foam in auxiliary
Under the synergistic effect of agent sodium sulfate of polyethenoxy ether of fatty alcohol, the foaming effect of lauryl sodium sulfate is more excellent, the gas generated
Bubble is finer and closely woven, is conducive to the mechanical property for improving material.More outstanding foaming can be played under the synergistic effect of the two
Effect.
Preferably, the A additive is polyvinyl alcohol.
Preferably, the B additive is polyethylene glycol.
Polyvinyl alcohol is a kind of high molecular material that safety is extremely outstanding, since it is with environmental-friendly and high biofacies
The characteristics of capacitive, therefore have application in biomaterial and field of tissue engineering technology, and it is water-soluble good, the knot with height
Crystalline substance, chemical stability, thermal stability and mechanical strength can greatly enhance matrix with the synergistic effect of composite sponge matrix
The mechanical property of material can make further raising being subject to polyethylene glycol cooperation to mechanical property.
Preferably, the A promotor is dibenzyl dithio amino methanol zinc.
Preferably, the B promotor is 2-steryl benzothiazole.
Dibenzyl dithio amino methanol zinc and 2-steryl benzothiazole belong to vulcanizing agent, wherein dibenzyl dithio
Amino methanol zinc is as a kind of conventional curing agent, and 2-steryl benzothiazole is a kind of sour sulfur agent, and curing temperature is lower, tool
There is medium curingprocess rate, itself has preferable sulfurization, can play good facilitation during the preparation process, and two
Benzyl dithiocarbamates methanol zinc can strengthen its vulcanization effect and sulphur significantly under the synergistic effect of 2-steryl benzothiazole
Change efficiency.
The beneficial effects of the present invention are:
1) the matrix used material of the present invention and wherein a large amount of components are green environmental protection degradable material, obtained product is also more
Add environmentally protective；
2) degradable high-elastic sponge has good biocompatibility, and preparation process and use process are non-hazardous to human body；
3) degradable high-elastic sponge has good chemical stability；
4) degradable high-elastic sponge has extremely outstanding mechanical property, extremely outstanding especially on elastic property.
Specific embodiment
Further clear detailed description explanation is made to the present invention below in conjunction with specific embodiment.
Embodiment 1
A kind of degradable high-elastic sponge, the degradable high-elastic sponge prepare the substance that raw material includes following parts by weight: multiple
100 parts of sponge matrix of conjunction, 3 parts by weight of polyvinyl alcohol, 4 parts by weight of polyethylene glycol, 0.5 parts by weight of zinc oxide, prodan 1.75
Parts by weight, 2.35 parts by weight of dibenzyl dithio amino methanol zinc and 1.1 parts by weight of 2-steryl benzothiazole；
Wherein the preparation method of the composite sponge matrix includes following preparation step:
1) ingredient: 1 parts by weight of bentonite, 80 parts by weight of acrylamide monomer, 25 parts by weight of polyvinyl alcohol, N, N- di-2-ethylhexylphosphine oxide third
5.5 parts by weight of acrylamide, 3 parts by weight of ammonium persulfate, 3.5 parts by weight of lauryl sodium sulfate, fatty alcohol polyoxyethylene ether sulfuric acid
0.35 parts by weight of sodium, 4 parts by weight of 3.5 parts by weight of maleic anhydride and ammonium hydroxide；
2) prepared by polymeric additive:
A) deionized water of maleic anhydride and its 50 times of parts by weight is mixed, is added to the instrument equipped with reflux condensate device
In, and simultaneously constant temperature is stirred to react 30min, revolving speed 500r/min is hydrolyzed to 60 DEG C under the conditions of 60 DEG C by oil bath heating
To maleic acid anhydride solution；
B) under condition of ice bath, ammonium hydroxide is added into the maleic acid anhydride solution that step a) is obtained, is warming up to after mixing evenly
85 DEG C, 175min, revolving speed 500r/min are reacted, imports drying under the conditions of 80 DEG C in porcelain container after reflection while hot,
The maleic anhydride ammonium salt of white solid is obtained after drying；
C) the maleic anhydride ammonium salt that step b) is obtained is placed in 150 DEG C of hot environment progress polymerization reaction 5h, it is poly-
Succinimide, and be ground to powdered；
D) powdered polysuccinimide obtained by step c) is added in excessive water, stirring and dissolving, with the hydrogen-oxygen of 0.5mol/L
Change sodium water solution and adjust pH value to 10.9,60min is hydrolyzed under 50 DEG C of water bath conditions, and water-soluble with the sodium hydroxide of 0.5mol/L
Liquid keeps hydrolytic process pH value to be maintained at 10.8, then to dehydrated alcohol is added in solution while stirring, generates brown oil liquid
It is slowly added dropwise after drop, until upper layer does not generate white opacity thing, concussion liquid separation is carried out to solution, sub-cloud liquid is placed in 120 DEG C
In environment dry to mass change per hour less than 0.5% to get arrive polymeric additive；
3) bentonite is dissolved in the deionized water of its 100 times of parts by weight, ultrasonic disperse 60min is carried out to it, is passed through nitrogen pair
It carries out purging 30min, makes its degassing；
4) acrylamide, polyvinyl alcohol, N, N- di-2-ethylhexylphosphine oxide are added in the bentonite aqueous dispersion to step 3) after degassed
Lauryl sodium sulfate is added after being uniformly mixed in the mixture of polymeric additive obtained by acrylamide and step 2)
Quickly stirring 15min is carried out with the revolving speed of 600r/min with sodium sulfate of polyethenoxy ether of fatty alcohol, then with the revolving speed of 120r/min
It carrying out mixing slowly 20min, ammonium persulfate is then added and starts to react, control is warming up to 75 DEG C and keeps 5h in reaction process,
It is rinsed after reaction with deionized water, and dry 48h under the conditions of 45 DEG C, obtains composite sponge matrix.
Embodiment 2
A kind of degradable high-elastic sponge, the degradable high-elastic sponge prepare the substance that raw material includes following parts by weight: multiple
100 parts of sponge matrix of conjunction, 5.5 parts by weight of polyvinyl alcohol, 9 parts by weight of polyethylene glycol, 1.1 parts by weight of zinc oxide, prodan
2.55 parts by weight, 4.5 parts by weight of dibenzyl dithio amino methanol zinc and 2.35 parts by weight of 2-steryl benzothiazole；
Wherein the preparation method of the composite sponge matrix includes following preparation step:
1) ingredient: 5 parts by weight of bentonite, 125 parts by weight of acrylamide monomer, 35 parts by weight of polyvinyl alcohol, N, N- di-2-ethylhexylphosphine oxide
12.5 parts by weight of acrylamide, 5 parts by weight of ammonium persulfate, 5.5 parts by weight of lauryl sodium sulfate, fatty alcohol polyoxyethylene ether sulphur
Sour 0.85 parts by weight of sodium, 7 parts by weight of 6 parts by weight of maleic anhydride and ammonium hydroxide；
2) prepared by polymeric additive:
A) deionized water of maleic anhydride and its 50 times of parts by weight is mixed, is added to the instrument equipped with reflux condensate device
In, and by oil bath heating, simultaneously constant temperature is stirred to react 35min, revolving speed 1000r/min to 60 DEG C under the conditions of 60 DEG C, hydrolyzes
Obtain maleic acid anhydride solution；
B) under condition of ice bath, ammonium hydroxide is added into the maleic acid anhydride solution that step a) is obtained, is warming up to after mixing evenly
85 DEG C, 200min, revolving speed 1000r/min are reacted, imports drying under the conditions of 85 DEG C in porcelain container after reflection while hot,
The maleic anhydride ammonium salt of white solid is obtained after drying；
C) the maleic anhydride ammonium salt that step b) is obtained is placed in 230 DEG C of hot environment progress polymerization reaction 1h, it is poly-
Succinimide, and be ground to powdered；
D) powdered polysuccinimide obtained by step c) is added in excessive water, stirring and dissolving, with the hydrogen-oxygen of 0.5mol/L
Change sodium water solution and adjust pH value to 11.2,80min is hydrolyzed under 50 DEG C of water bath conditions, and water-soluble with the sodium hydroxide of 0.5mol/L
Liquid keeps hydrolytic process pH value to be maintained at 11.2, then to dehydrated alcohol is added in solution while stirring, generates brown oil liquid
It is slowly added dropwise after drop, until upper layer does not generate white opacity thing, concussion liquid separation is carried out to solution, sub-cloud liquid is placed in 130 DEG C
In environment dry to mass change per hour less than 0.5% to get arrive polymeric additive；
3) bentonite is dissolved in the deionized water of its 120 times of parts by weight, ultrasonic disperse 80min is carried out to it, is passed through nitrogen pair
It carries out purging 35min, makes its degassing；
4) acrylamide, polyvinyl alcohol, N, N- di-2-ethylhexylphosphine oxide are added in the bentonite aqueous dispersion to step 3) after degassed
Lauryl sodium sulfate is added after being uniformly mixed in the mixture of polymeric additive obtained by acrylamide and step 2)
Quickly stirring 20min is carried out with the revolving speed of 800r/min with sodium sulfate of polyethenoxy ether of fatty alcohol, then with the revolving speed of 180r/min
It carrying out mixing slowly 30min, ammonium persulfate is then added and starts to react, control is warming up to 75 DEG C and keeps 6h in reaction process,
It is rinsed after reaction with deionized water, and dry 50h under the conditions of 50 DEG C, obtains composite sponge matrix.
Embodiment 3
A kind of degradable high-elastic sponge, the degradable high-elastic sponge prepare the substance that raw material includes following parts by weight: multiple
100 parts of sponge matrix of conjunction, 3.95 parts by weight of polyvinyl alcohol, 6.75 parts by weight of polyethylene glycol, 0.8 parts by weight of zinc oxide, fluosilicic acid
1.95 parts by weight of sodium, 3.15 parts by weight of dibenzyl dithio amino methanol zinc and 1.9 parts by weight of 2-steryl benzothiazole；
Wherein the preparation method of the composite sponge matrix includes following preparation step:
1) ingredient: 3.5 parts by weight of bentonite, 105 parts by weight of acrylamide monomer, 31 parts by weight of polyvinyl alcohol, N, N- methylene
8.75 parts by weight of bisacrylamide, 3.5 parts by weight of ammonium persulfate, 5 parts by weight of lauryl sodium sulfate, fatty alcohol polyoxyethylene ether
0.75 parts by weight of sodium sulphate, 5.5 parts by weight of 4.55 parts by weight of maleic anhydride and ammonium hydroxide；
2) prepared by polymeric additive:
A) deionized water of maleic anhydride and its 50 times of parts by weight is mixed, is added to the instrument equipped with reflux condensate device
In, and simultaneously constant temperature is stirred to react 30min, revolving speed 800r/min is hydrolyzed to 60 DEG C under the conditions of 60 DEG C by oil bath heating
To maleic acid anhydride solution；
B) under condition of ice bath, ammonium hydroxide is added into the maleic acid anhydride solution that step a) is obtained, is warming up to after mixing evenly
85 DEG C, 180min, revolving speed 600r/min are reacted, imports drying under the conditions of 85 DEG C in porcelain container after reflection while hot,
The maleic anhydride ammonium salt of white solid is obtained after drying；
C) the maleic anhydride ammonium salt that step b) is obtained is placed in progress polymerization reaction 2.5h in 200 DEG C of hot environment,
Polysuccinimide, and be ground to powdered；
D) powdered polysuccinimide obtained by step c) is added in excessive water, stirring and dissolving, with the hydrogen-oxygen of 0.5mol/L
Change sodium water solution and adjust pH value to 11, hydrolyzes 60min, and under 50 DEG C of water bath conditions with the sodium hydrate aqueous solution of 0.5mol/L
Hydrolytic process pH value is kept to be maintained at 11, then to being added dehydrated alcohol in solution while stirring, after generating brown oil drop
It is slowly added dropwise, until upper layer does not generate white opacity thing, concussion liquid separation is carried out to solution, sub-cloud liquid is placed in 125 DEG C of environment
Middle drying to mass change per hour less than 0.5% to get arrive polymeric additive；
3) bentonite is dissolved in the deionized water of its 110 times of parts by weight, ultrasonic disperse 60min is carried out to it, is passed through nitrogen pair
It carries out purging 35min, makes its degassing；
4) acrylamide, polyvinyl alcohol, N, N- di-2-ethylhexylphosphine oxide are added in the bentonite aqueous dispersion to step 3) after degassed
Lauryl sodium sulfate is added after being uniformly mixed in the mixture of polymeric additive obtained by acrylamide and step 2)
Quickly stirring 20min is carried out with the revolving speed of 700r/min with sodium sulfate of polyethenoxy ether of fatty alcohol, then with the revolving speed of 150r/min
It carrying out mixing slowly 30min, ammonium persulfate is then added and starts to react, control is warming up to 75 DEG C and keeps 6h in reaction process,
It is rinsed after reaction with deionized water, and dry 48h under the conditions of 45 DEG C, obtains composite sponge matrix.
Embodiment 4
A kind of degradable high-elastic sponge, the degradable high-elastic sponge prepare the substance that raw material includes following parts by weight: multiple
100 parts of sponge matrix of conjunction, 4.25 parts by weight of polyvinyl alcohol, 7.5 parts by weight of polyethylene glycol, 1.05 parts by weight of zinc oxide, fluosilicic acid
2.15 parts by weight of sodium, 3.5 parts by weight of dibenzyl dithio amino methanol zinc and 2.15 parts by weight of 2-steryl benzothiazole；
Wherein the preparation method of the composite sponge matrix includes following preparation step:
1) ingredient: 3.5 parts by weight of bentonite, 105 parts by weight of acrylamide monomer, 31 parts by weight of polyvinyl alcohol, N, N- methylene
8.75 parts by weight of bisacrylamide, 3.5 parts by weight of ammonium persulfate, 5 parts by weight of lauryl sodium sulfate, fatty alcohol polyoxyethylene ether
0.75 parts by weight of sodium sulphate, 5.5 parts by weight of 4.55 parts by weight of maleic anhydride and ammonium hydroxide；
2) prepared by polymeric additive:
A) deionized water of maleic anhydride and its 50 times of parts by weight is mixed, is added to the instrument equipped with reflux condensate device
In, and simultaneously constant temperature is stirred to react 30min, revolving speed 800r/min is hydrolyzed to 60 DEG C under the conditions of 60 DEG C by oil bath heating
To maleic acid anhydride solution；
B) under condition of ice bath, ammonium hydroxide is added into the maleic acid anhydride solution that step a) is obtained, is warming up to after mixing evenly
85 DEG C, 180min, revolving speed 600r/min are reacted, imports drying under the conditions of 85 DEG C in porcelain container after reflection while hot,
The maleic anhydride ammonium salt of white solid is obtained after drying；
C) the maleic anhydride ammonium salt that step b) is obtained is placed in progress polymerization reaction 2.5h in 200 DEG C of hot environment,
Polysuccinimide, and be ground to powdered；
D) powdered polysuccinimide obtained by step c) is added in excessive water, stirring and dissolving, with the hydrogen-oxygen of 0.5mol/L
Change sodium water solution and adjust pH value to 11, hydrolyzes 60min, and under 50 DEG C of water bath conditions with the sodium hydrate aqueous solution of 0.5mol/L
Hydrolytic process pH value is kept to be maintained at 11, then to being added dehydrated alcohol in solution while stirring, after generating brown oil drop
It is slowly added dropwise, until upper layer does not generate white opacity thing, concussion liquid separation is carried out to solution, sub-cloud liquid is placed in 125 DEG C of environment
Middle drying to mass change per hour less than 0.5% to get arrive polymeric additive；
3) bentonite is dissolved in the deionized water of its 110 times of parts by weight, ultrasonic disperse 60min is carried out to it, is passed through nitrogen pair
It carries out purging 35min, makes its degassing；
4) acrylamide, polyvinyl alcohol, N, N- di-2-ethylhexylphosphine oxide are added in the bentonite aqueous dispersion to step 3) after degassed
Lauryl sodium sulfate is added after being uniformly mixed in the mixture of polymeric additive obtained by acrylamide and step 2)
Quickly stirring 20min is carried out with the revolving speed of 700r/min with sodium sulfate of polyethenoxy ether of fatty alcohol, then with the revolving speed of 150r/min
It carrying out mixing slowly 30min, ammonium persulfate is then added and starts to react, control is warming up to 75 DEG C and keeps 6h in reaction process,
It is rinsed after reaction with deionized water, and dry 48h under the conditions of 45 DEG C, obtains composite sponge matrix.
Embodiment 5
A kind of degradable high-elastic sponge, the degradable high-elastic sponge prepare the substance that raw material includes following parts by weight: multiple
100 parts of sponge matrix of conjunction, 4.05 parts by weight of polyvinyl alcohol, 7.1 parts by weight of polyethylene glycol, 0.95 parts by weight of zinc oxide, fluosilicic acid
2.05 parts by weight of sodium, 3.35 parts by weight of dibenzyl dithio amino methanol zinc and 1.95 parts by weight of 2-steryl benzothiazole；
Wherein the preparation method of the composite sponge matrix includes following preparation step:
1) ingredient: 3.5 parts by weight of bentonite, 105 parts by weight of acrylamide monomer, 31 parts by weight of polyvinyl alcohol, N, N- methylene
8.75 parts by weight of bisacrylamide, 3.5 parts by weight of ammonium persulfate, 5 parts by weight of lauryl sodium sulfate, fatty alcohol polyoxyethylene ether
0.75 parts by weight of sodium sulphate, 5.5 parts by weight of 4.55 parts by weight of maleic anhydride and ammonium hydroxide；
2) prepared by polymeric additive:
A) deionized water of maleic anhydride and its 50 times of parts by weight is mixed, is added to the instrument equipped with reflux condensate device
In, and simultaneously constant temperature is stirred to react 30min, revolving speed 800r/min is hydrolyzed to 60 DEG C under the conditions of 60 DEG C by oil bath heating
To maleic acid anhydride solution；
B) under condition of ice bath, ammonium hydroxide is added into the maleic acid anhydride solution that step a) is obtained, is warming up to after mixing evenly
85 DEG C, 180min, revolving speed 600r/min are reacted, imports drying under the conditions of 85 DEG C in porcelain container after reflection while hot,
The maleic anhydride ammonium salt of white solid is obtained after drying；
C) the maleic anhydride ammonium salt that step b) is obtained is placed in progress polymerization reaction 2.5h in 200 DEG C of hot environment,
Polysuccinimide, and be ground to powdered；
D) powdered polysuccinimide obtained by step c) is added in excessive water, stirring and dissolving, with the hydrogen-oxygen of 0.5mol/L
Change sodium water solution and adjust pH value to 11, hydrolyzes 60min, and under 50 DEG C of water bath conditions with the sodium hydrate aqueous solution of 0.5mol/L
Hydrolytic process pH value is kept to be maintained at 11, then to being added dehydrated alcohol in solution while stirring, after generating brown oil drop
It is slowly added dropwise, until upper layer does not generate white opacity thing, concussion liquid separation is carried out to solution, sub-cloud liquid is placed in 125 DEG C of environment
Middle drying to mass change per hour less than 0.5% to get arrive polymeric additive；
3) bentonite is dissolved in the deionized water of its 110 times of parts by weight, ultrasonic disperse 60min is carried out to it, is passed through nitrogen pair
It carries out purging 35min, makes its degassing；
4) acrylamide, polyvinyl alcohol, N, N- di-2-ethylhexylphosphine oxide are added in the bentonite aqueous dispersion to step 3) after degassed
Lauryl sodium sulfate is added after being uniformly mixed in the mixture of polymeric additive obtained by acrylamide and step 2)
Quickly stirring 20min is carried out with the revolving speed of 700r/min with sodium sulfate of polyethenoxy ether of fatty alcohol, then with the revolving speed of 150r/min
It carrying out mixing slowly 30min, ammonium persulfate is then added and starts to react, control is warming up to 75 DEG C and keeps 6h in reaction process,
It is rinsed after reaction with deionized water, and dry 48h under the conditions of 45 DEG C, obtains composite sponge matrix.
The degradable high-elastic sponge of Examples 1 to 5 is detected, partial detection is as shown in the table.
By upper table it will be evident that degradable high-elastic sponge of the invention has very good mechanical property.
Claims (10)
1. a kind of degradable high-elastic sponge, which is characterized in that the raw material for preparing of the degradable high-elastic sponge includes following weight
The substance of number: 100 parts of composite sponge matrix, 3~5.5 parts by weight of A additive, 4~9 parts by weight of B additive, zinc oxide 0.5
~1.1 parts by weight, 1.75~2.55 parts by weight of prodan, 2.35~4.5 parts by weight of A promotor and B promotor 1.1~2.35
Parts by weight.
2. the degradable high-elastic sponge of one kind according to claim 1, which is characterized in that the system of the degradable high-elastic sponge
Standby raw material includes the substance of following parts by weight: 100 parts of composite sponge matrix, 3.95~4.25 parts by weight of A additive, and B addition
6.75~7.5 parts by weight of agent, 0.8~1.05 parts by weight of zinc oxide, 1.95~2.15 parts by weight of prodan, A promotor 3.15
1.9~2.15 parts by weight of~3.5 parts by weight and B promotor.
3. the degradable high-elastic sponge of one kind according to claim 1, which is characterized in that the system of the degradable high-elastic sponge
Standby raw material includes the substance of following parts by weight: 100 parts of composite sponge matrix, 4.05 parts by weight of A additive, and 7.1 weight of B additive
Measure part, 0.95 parts by weight of zinc oxide, 2.05 parts by weight of prodan, 1.95 weight of 3.35 parts by weight of A promotor and B promotor
Part.
4. the degradable high-elastic sponge of one kind according to claim 1 or 2 or 3, which is characterized in that the composite sponge matrix
Preparation method include following preparation step:
1) prepared by polymeric additive:
A) deionized water of maleic anhydride and its 50 times of parts by weight is mixed, is added to the instrument equipped with reflux condensate device
In, and simultaneously constant temperature is stirred to react 30~35min to 60 DEG C under the conditions of 60 DEG C by oil bath heating, revolving speed is 500~1000r/
Min, hydrolysis obtain maleic acid anhydride solution；
B) under condition of ice bath, ammonium hydroxide is added into the maleic acid anhydride solution that step a) is obtained, is warming up to after mixing evenly
85 DEG C, 175~200min is reacted, revolving speed is 500~1000r/min, imported while hot after reflection in porcelain container 80~
It is dry under the conditions of 85 DEG C, the maleic anhydride ammonium salt of white solid is obtained after dry；
C) by the maleic anhydride ammonium salt that step b) is obtained be placed in 150~230 DEG C of hot environment carry out polymerization reaction 1~
5h, polysuccinimide, and be ground to powdered；
D) powdered polysuccinimide obtained by step c) is added in excessive water, stirring and dissolving, with the hydrogen-oxygen of 0.5mol/L
Change sodium water solution adjusting pH value and hydrolyze 60~80min under 50 DEG C of water bath conditions to 10.9~11.2, and with the hydrogen of 0.5mol/L
Aqueous solution of sodium oxide keeps hydrolytic process pH value to be maintained at 10.8~11.2, then to anhydrous second is added in solution while stirring
Alcohol is slowly added dropwise after generating brown oil drop, until upper layer does not generate white opacity thing, carries out concussion liquid separation to solution, goes
Lower liquid is placed in dry in 120~130 DEG C of environment to mass change per hour and add less than 0.5% to get to macromolecule
Agent；
2) bentonite is dissolved in the deionized water of its 100~120 times of parts by weight, 60~80min of ultrasonic disperse is carried out to it, led to
Enter nitrogen and 30~35min of purging is carried out to it, makes its degassing；
3) acrylamide, polyvinyl alcohol, N, N- di-2-ethylhexylphosphine oxide are added in the bentonite aqueous dispersion to step 2) after degassed
Lauryl sodium sulfate is added after being uniformly mixed in the mixture of polymeric additive obtained by acrylamide and step 1)
Quickly 15~20min of stirring is carried out with the revolving speed of 600~800r/min with auxiliary blowing agent, then is turned with 120~180r/min
Speed carries out mixing slowly 20~30min, and ammonium persulfate is then added and starts to react, control is warming up to 75 DEG C and protects in reaction process
5~6h is held, is rinsed after reaction with deionized water, and dry 48~50h under the conditions of 45~50 DEG C, obtains composite sponge base
Body.
5. the degradable high-elastic sponge of one kind according to claim 4, which is characterized in that used in the composite sponge matrix
The mass fraction proportion of raw material is 1~5 parts by weight of bentonite, 80~125 parts by weight of acrylamide monomer, polyvinyl alcohol 25~35
Parts by weight, N, 5.5~12.5 parts by weight of N- methylene-bisacrylamide, 3~5 parts by weight of ammonium persulfate, lauryl sodium sulfate
3.5~5.5 parts by weight, 0.35~0.85 parts by weight of auxiliary blowing agent, 3.5~6 parts by weight of maleic anhydride and ammonium hydroxide 4~7
Parts by weight.
6. the degradable high-elastic sponge of one kind according to claim 5, which is characterized in that the auxiliary blowing agent is fatty alcohol
Polyethenoxy ether sodium sulfate.
7. the degradable high-elastic sponge of one kind according to claim 1 or 2 or 3, which is characterized in that the A additive is poly-
Vinyl alcohol.
8. the degradable high-elastic sponge of one kind according to claim 1 or 2 or 3, which is characterized in that the B additive is poly-
Ethylene glycol.
9. the degradable high-elastic sponge of one kind according to claim 1 or 2 or 3, which is characterized in that the A promotor is two
Benzyl dithiocarbamates methanol zinc.
10. the degradable high-elastic sponge of one kind according to claim 1 or 2 or 3, which is characterized in that the B promotor is 2-
Mercapto alcohol radical benzothiazole.
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| WO2011099087A1 (en) * | 2010-02-15 | 2011-08-18 | 甲陽ケミカル株式会社 | Chitin-derived sponge hemostatic material and method for producing same |
| CN107652482A (en) * | 2017-10-18 | 2018-02-02 | 德清舒华泡沫座椅有限公司 | A kind of degradable high-elastic sponge and its preparation technology |
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