CN105669905A - Preparation method of intumescent flame retardant synergist adopting saccharide derivatives - Google Patents
Preparation method of intumescent flame retardant synergist adopting saccharide derivatives Download PDFInfo
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- CN105669905A CN105669905A CN201610051449.XA CN201610051449A CN105669905A CN 105669905 A CN105669905 A CN 105669905A CN 201610051449 A CN201610051449 A CN 201610051449A CN 105669905 A CN105669905 A CN 105669905A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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Abstract
The invention discloses a preparation method of an intumescent flame retardant synergist adopting saccharide derivatives and belongs to the technical field of flame retardant materials. The method comprises steps as follows: 1) a high-carbon graft polymer is prepared from chitosan graft polyacrylic acid; 2) N-acetylated chitosan graft polyacrylic acid is prepared, that is, solid chitosan graft polyacrylic acid is dissolved in an acetic acid aqueous solution, 1,2-propylene glycol is added, the mixture is left to stand at the room temperature for degassing for 1 days, and a degassed mixed liquid is obtained; an acetylated solution is slowly added to the degassed mixed liquid through a constant-pressure dropping funnel, the mixture is stirred at the room temperature to react for 5 h, the obtained solution is adjusted to be alkaline with 1 mol/L of sodium hydroxide after the reaction, and an N-acetylated chitosan graft polyacrylic acid aqueous solution is obtained; 3) solid N-acetylated chitosan graft polyacrylic acid, namely, the intumescent flame retardant synergist adopting saccharide derivatives, can be obtained through evaporative crystallization and drying. The preparation method adopts the simple and green process, and the prepared flame retardant synergist is efficient and environment-friendly.
Description
Technical field
The invention belongs to fire proofing technical field, the preparation method being specifically related to a kind of carbohydrate derivative expansion type flame-retarding synergist.
Background technology
In the world every year due to the fire that synthesis macromolecule or natural macromolecular material cause, the mass casualties caused and huge economic loss. In order to reduce odds and the degree of danger of fire, a lot of occasions are required to use fire proofing, and have formulated many flame-retardant standards, method of testing and specification. What employ up in the early time is halogen flame, because halogen flame is good with the macromolecular material compatibility, good flame retardation effect, once the parent being once subject to user looks at, but this based flame retardant there is also fatal shortcoming, the polymer adopting halogen flame fire-retardant produces substantial amounts of toxic gas, corrosive gas and smog in combustion, making the people in scene of fire have not enough time to withdraw burning things which may cause a fire disaster and be first choked to death by poison, its hazard ratio big fire is inherently more seriously. Therefore, people have to, and searching is a kind of does not produce the fire retardant that toxic gas, corrosive gas and generation smog are few in combustion, and expansion type flame retardant just overcomes one of disadvantages mentioned above fire retardant becoming people's attention. Expansion type flame retardant is non-volatile when burning, do not produce toxic gas, is referred to as nuisanceless fire retardant, is the trend of fire retardant industry development.
Abroad there is commercial expandable flame retardant type additive at present, owing to being used mostly the expensive of tetramethylolmethane (PER) raw material, caused on the high side. U.S.'s Borg-Warner chemical company is developed into the phosphoric melamine salt expansion type flame retardant of cage structure simultaneously, but owing to the synthesis yield of this fire retardant is very low, causes that manufacturing cost is higher. Domestic once saw with starch as the research of the expansion type flame retardant in charcoal source, and with cheap starch replacement PER, the cost of expanding fire retardant can be made to be substantially reduced. We, with starch for inspiring, have invented a kind of preparation technology being the expansion type flame retardant in charcoal source with glucides such as Chitosan-phospholipid complex, sodium alginate, guar gum and gluconic acids.
Summary of the invention
Goal of the invention: the preparation method that it is an object of the invention to provide a kind of carbohydrate derivative expansion type flame-retarding synergist, is used as the succedaneum of halogen containing flame-retardant, provides flame-retarded technology more green, cleaning for environmental conservation and human health.
For achieving the above object, the present invention adopts the following technical scheme that
The preparation method of a kind of carbohydrate derivative expansion type flame-retarding synergist, it is characterised in that comprise the steps:
1) high-carbon quantity graft copolymer prepared by chitosan graft polyacrylic acid
Adopt mechanical agitation, with water for solvent, chitosan is dissolved in water, the chitosan aqueous solution that preparation is required; The chitosan aqueous solution of above-mentioned preparation is placed in 50～100 DEG C of oil baths, with being 1:6～1:10 according to chitosan and acrylic acid mass ratio after nitrogen emptying air, acrylic acid is added drop-wise in reaction mixture by constant pressure funnel, after fully mixing, drip initiator by constant pressure funnel, after dropwising, continue to use nitrogen deoxidation, insulation reaction 5～10 hours, stopped reaction; Precipitate with concentrated hydrochloric acid, filtering, solid mass fraction is decompression sucking filtration or to adopt ethanol be filtration under diminished pressure after solvent apparatus,Soxhlet's extracting 2 days after 99% washing with alcohol three times, removes acrylate homopolymer, after 50 DEG C of vacuum dryings, obtain solid chitosan grafted polyacrylic acid;
2) N-Acetylated Chitosans grafted polyacrylic acid is prepared
0.5g solid chitosan grafted polyacrylic acid is dissolved in the acetic acid aqueous solution of 50mL0.5wt%, adds 30～100mL1,2-propylene glycol and left at room temperature degasification 1 day, obtain the mixed liquor after degasification; It is slowly added to acetylation solution in the mixed liquor after degasification by constant pressure funnel, stirring reaction 5 hours under room temperature, after stopped reaction, gained solution 1mol/L sodium hydroxide is adjusted to alkalescence, obtains N-Acetylated Chitosans graft polypropylene aqueous acid;
3) evaporative crystallization dries
After N-Acetylated Chitosans graft polypropylene aqueous acid is accelerated distilled water dialysis 2 days with magneton stirring; evaporative crystallization; last 50 DEG C of vacuum dryings, it is possible to obtain solid N-Acetylated Chitosans grafted polyacrylic acid, be carbohydrate derivative expansion type flame-retarding synergist.
Step 1) in, described initiator is selected from sodium sulfite, ammonium ceric nitrate and hydrogen peroxide.
Described initiator is 3.28 × 10-3～6 × 10-3The ammonium ceric nitrate of mol/L.
Step 2) in, described acetylation solution includes 10mL1,2-propylene glycol and 20mL acetic anhydride.
Beneficial effect: compared with prior art, the preparation method of a kind of carbohydrate derivative expansion type flame-retarding synergist of the present invention, not only technique is simple, green, and the fire retarding synergist produced is efficient, environmental protection; This carbohydrate derivative expansion type flame-retarding synergist belongs to the category of halogen-free flame retardants simultaneously, in combustion because expansion type flame-retarding synergist produces a large amount of coke, the release of harmful gas can be reduced, effectively stop heat and the oxygen transmission in combustion zone Yu non-burning district; Relatively simple chitosan, the fusion temperature of the carbohydrate derivative expansion type flame-retarding synergist of this disclosed invention relatively early (starts fusing about 270 DEG C, and pure chitosan starts fusing at about 350 DEG C), fusion enthalpy is bigger than pure chitosan, so by fusion temperature in advance and the increase of fusion enthalpy, all may result in burning to terminate in pre-set time, and then reach fireproof purpose in the maximally effective time.
Accompanying drawing explanation
Fig. 1 is differential thermogravimetric analysis (TGA-DSC) curve of carbohydrate derivative expansion type flame-retarding synergist and compound polyurethane material;
Fig. 2 is the water absorption rate curve of carbohydrate derivative expansion type flame-retarding synergist and compound polyurethane material.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is described further.
The preparation method of a kind of carbohydrate derivative expansion type flame-retarding synergist and the application in aqueous polyurethane emulsion thereof, specifically comprise the following steps that
1) high-carbon quantity graft copolymer is prepared
The polyacrylic reaction of chitosan graft is with water for solvent, and it is placed in 50～100 DEG C of oil baths, with after nitrogen emptying air by ratio according to 1:6～1:10 (w/w) of chitosan and acrylic acid, acrylic acid is slowly added dropwise in reaction mixture by constant pressure funnel, after fully mixing, it is slowly added dropwise into 3.28 × 10 by constant pressure funnel-3～6 × 10-3Ammonium ceric nitrate (the Ce of mol/L4+) as initiator, after dropwising, continue to use nitrogen deoxidation, maintain original thermotonus 5～10 hours, stopped reaction. Then precipitate with concentrated hydrochloric acid, subsequently solution is filtered, solid mass fraction is the sucking filtration (or adopt ethanol be filtration under diminished pressure after solvent apparatus,Soxhlet's extracting 2 days) that reduces pressure after 99% washing with alcohol three times, remove acrylate homopolymer, after 50 DEG C of vacuum dryings, obtain solid chitosan grafted polyacrylic acid (CS-g-PAA), standby after being ground into powder. Initiator is selected from sodium sulfite, ammonium ceric nitrate and hydrogen peroxide.
2) water soluble graft copolymerization thing is prepared
The N-acetylation of CS-g-PAA carries out slight modification in homogeneous system. CS-g-PAA (0.5g) is dissolved in the acetic acid aqueous solution of 0.5wt% (50mL). Add 30～100mL1,2-propylene glycol and left at room temperature degasification 1 day. It is slowly added to acetylation solution (containing 10mL1,2-propylene glycol and 20mL acetic anhydride) in reaction mixture, stirring 5 hours under room temperature by constant pressure funnel. Gained solution 1mol/L sodium hydroxide regulates pH to 7～13. After dialysing with distilled water, evaporative crystallization, last 50 DEG C of vacuum dryings, it is possible to obtain N-acetylation CS-g-PAA (being called for short CP-N) solid, standby after grind into powder.
3) water soluble derivatives of chitosan extinguishing waterborn polyurethane emulsion is prepared
After preparation IPDI Waterborne Polyurethane Prepolymer, the water-soluble chitosan derivatives of synthesis is put in water according to setting ratio, then Waterborne Polyurethane Prepolymer is distributed to water-soluble chitosan derivative solution carries out blended, finally obtain water soluble derivatives of chitosan extinguishing waterborn polyurethane emulsion. When adding water-soluble chitosan, extinguishing waterborn polyurethane film forming is very poor, but when water-soluble chitosan addition reaches 0.4wt% soon, extinguishing waterborn polyurethane film forming improves, and the complete film forming of energy, do not have the situation of be full of cracks.
In embodiment, CP0-N refers to water-soluble chitosan; CP0-N/PU refers to: water-soluble chitosan extinguishing waterborn polyurethane composite; PU refers to: polyurethane; LOI refers to: limited oxygen index; Tensilestrength (Mpa): hot strength (unit Mpa); Elongationatbreak (%): elongation at break; Young ' smodulus (Mpa): Young's modulus (Mpa).
As shown in Fig. 1 (a), under 50～500 DEG C of nitrogen atmospheres, thermogravimetric analysis test is carried out with the heating rate of 20 DEG C/min, it can be seen that along with the increase of CP0-N content, when final temperature 500 DEG C, residue carbon residue content increases also with the increase of CP0-N, and this illustrates that CP0-N can generate layer of charcoal in the process of reaction, it is attached to the surface of polyurethane, to stop polyurethane-base bottom material to be burnt further.Fig. 1 (b) observes, the addition of CP0-N, the absorption heat making CP0-N/PU substantially increases, fusing is started at 270 DEG C, substantially can be seen that a melting hump, and about 350 DEG C it is observed that melting hump in the DSC figure of water-based polyurethane, this also illustrates that adding CP0-N can make the burning of polyurethane be reduced to below ignition point by melting absorption heat in advance. Can observe in CP0-N/PU figure that 3 absorb thermal spike simultaneously, respectively 270 DEG C, 320 DEG C and 440 DEG C. In the decomposition that the endothermic peaks of 320 DEG C are likely due in CP0-N hydroxyl or carboxyl, and it is likely due to the decomposition of amide groups or carbon skeleton at the absworption peak of 440 DEG C. In a word, adding CP0-N can increase the residue carbon residue of thermal decomposition process, has blocked the transmission of oxygen; By the decomposition of self functional group, a large amount of absorptions heat around, reduce further the transmission of the heat of polyurethane-base bottom material, and then stop spreading further of burning; Can also be observed that CP0-N/PU melting hump is than pure polyurethane about 100 DEG C in advance, because fusing needs to absorb substantial amounts of heat, so this can stop the further transmission of heat in advance.
From Fig. 2 it is observed that along with the increase of CP0-N content, the water absorption rate of CP0-N/PU is consequently increased, this is possibly due to CP0-N and contains substantial amounts of hydrophilic group, and hydrophilic group is certainly stronger in conjunction with the ability of Free water, occurs so just having above-mentioned phenomenon.
The mechanical strength of table 1 water soluble derivatives of chitosan extinguishing waterborn polyurethane and limited oxygen index
As shown in Table 1, along with the increase of CP0-N content, the hot strength of polyurethane and elongation at break are all on a declining curve, but the speed that hot strength declines does not have elongation at break fast, this illustrates that the hot strength of polyurethane film is had impact by CP0-N content, but general impacts are not as big. And CP0-N1/PU can not film forming, only CP0-N3/PU just can film forming. Film forming that can not be very complete when CP0-N addition is fewer, only when CP0-N content increases to a certain degree, just can complete film forming. This illustrates that adding CP0-N can produce be separated with PU, and now the fragility of material and hardness are occupied an leading position, and the hardness of material substantially increases. Young's modulus is the physical quantity describing solid material opposing deformability. It can be seen that addition CP0-N is more many, the Young's modulus of composite is more big, and rigidity is more strong, namely represents that the ability that material deforms upon is more little. This causes after being likely to be due to addition CP0-N that PU dispersion is uneven, and after causing solidification, cross-linked structure is uneven.
Limited oxygen index is widely used in assessment macromolecular material fire resistance. Limited oxygen index is defined as effectively supporting the minimum oxygen content of burning. When limited oxygen index is more than 26, macromolecular material now is considered as fire proofing. IPDI polyurethane is belonging to the highly flammable material with molten drop, and limited oxygen index only has 19. Comparing pure polyurethane material, CP0-N/PU composite has better flame resistance. The fire resistance of CP0-N/PU composite substantially improves along with the increase of CP0-N content. When polyurethane material contains 0.35wt%, its limited oxygen index can reach 23.6. Comparing pure polyurethane, the increment of LOI reaches 4.6. Now CP0-N/PU composite has occurred without molten drop when doing limited oxygen index test, but coke layer occurs. Therefore CP0-N demonstrates the high flame retarding efficiency of comparison and anti-molten drop character. Non-oxygen character gas that flame-retardant nature so good for CP0-N decomposites owing to N element and the decomposition of carbon skeleton.When CP0-N burns at low temperatures, amino can burn the gas generating the burning of the non-supporting such as ammonia and fusing absorbs substantial amounts of heat and stops proceeding of burning further; Carbon skeleton can burn and generate the anti-flammability jointly stoping the carrying out of polyurethane burning to improve CP0-N/PU composite that interacts of the coke layer being attached to polyurethane surface, N element and carbon skeleton.
The above chitosan material used all can replace with sodium alginate, guar gum and gluconic acid, adopts similar technique to synthesize similar carbohydrate derivative expansion type flame-retarding synergist, and its flame retardant effect can reach same efficient result. The hot strength of polyurethane material is not had too much influence by it simultaneously, is that one is close to perfect expansion type flame-retarding synergist.
Claims (4)
1. the preparation method of a carbohydrate derivative expansion type flame-retarding synergist, it is characterised in that comprise the steps:
1) high-carbon quantity graft copolymer prepared by chitosan graft polyacrylic acid
Adopt mechanical agitation, with water for solvent, chitosan is dissolved in water, the chitosan aqueous solution that preparation is required; The chitosan aqueous solution of above-mentioned preparation is placed in 50～100 DEG C of oil baths, with being 1:6～1:10 according to chitosan and acrylic acid mass ratio after nitrogen emptying air, acrylic acid is added drop-wise in reaction mixture by constant pressure funnel, after fully mixing, drip initiator by constant pressure funnel, after dropwising, continue to use nitrogen deoxidation, insulation reaction 5～10 hours, stopped reaction; Precipitate with concentrated hydrochloric acid, filtering, solid mass fraction is decompression sucking filtration or to adopt ethanol be filtration under diminished pressure after solvent apparatus,Soxhlet's extracting 2 days after 99% washing with alcohol three times, removes acrylate homopolymer, after 50 DEG C of vacuum dryings, obtain solid chitosan grafted polyacrylic acid;
2) N-Acetylated Chitosans grafted polyacrylic acid is prepared
0.5g solid chitosan grafted polyacrylic acid is dissolved in the acetic acid aqueous solution of 50mL0.5wt%, adds 30～100mL1,2-propylene glycol and left at room temperature degasification 1 day, obtain the mixed liquor after degasification; It is slowly added to acetylation solution in the mixed liquor after degasification by constant pressure funnel, stirring reaction 5 hours under room temperature, after stopped reaction, gained solution 1mol/L sodium hydroxide is adjusted to alkalescence, obtains N-Acetylated Chitosans graft polypropylene aqueous acid;
3) evaporative crystallization dries
After N-Acetylated Chitosans graft polypropylene aqueous acid is accelerated distilled water dialysis 2 days with magneton stirring; evaporative crystallization; last 50 DEG C of vacuum dryings, it is possible to obtain solid N-Acetylated Chitosans grafted polyacrylic acid, be carbohydrate derivative expansion type flame-retarding synergist.
2. the preparation method of carbohydrate derivative expansion type flame-retarding synergist according to claim 1, it is characterised in that: step 1) in, described initiator is selected from sodium sulfite, ammonium ceric nitrate and hydrogen peroxide.
3. the preparation method of carbohydrate derivative expansion type flame-retarding synergist according to claim 2, it is characterised in that: described initiator is 3.28 × 10-3～6 × 10-3The ammonium ceric nitrate of mol/L.
4. the preparation method of carbohydrate derivative expansion type flame-retarding synergist according to claim 1, it is characterised in that: step 2) in, described acetylation solution includes 10mL1,2-propylene glycol and 20mL acetic anhydride.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110483663A (en) * | 2019-08-14 | 2019-11-22 | 东南大学 | A kind of modification of chitosan fire retardant and preparation method thereof |
| CN112029157A (en) * | 2020-08-06 | 2020-12-04 | 湖北工程学院 | Anti-dripping composite intumescent flame retardant and preparation method and application thereof |
| CN114644903A (en) * | 2022-04-11 | 2022-06-21 | 安徽省奥佳建材有限公司 | Self-adhesive waterproof roll cementing material and waterproof roll prepared from same |
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| JP2010083996A (en) * | 2008-09-30 | 2010-04-15 | Kurita Water Ind Ltd | Manufacturing method for graft polymerization substance |
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| JP2010083996A (en) * | 2008-09-30 | 2010-04-15 | Kurita Water Ind Ltd | Manufacturing method for graft polymerization substance |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110483663A (en) * | 2019-08-14 | 2019-11-22 | 东南大学 | A kind of modification of chitosan fire retardant and preparation method thereof |
| CN110483663B (en) * | 2019-08-14 | 2021-06-11 | 东南大学 | Modified chitosan flame retardant and preparation method thereof |
| CN112029157A (en) * | 2020-08-06 | 2020-12-04 | 湖北工程学院 | Anti-dripping composite intumescent flame retardant and preparation method and application thereof |
| CN114644903A (en) * | 2022-04-11 | 2022-06-21 | 安徽省奥佳建材有限公司 | Self-adhesive waterproof roll cementing material and waterproof roll prepared from same |
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