CN109517188A - A kind of biology base composite flame-retardant agent and its application - Google Patents

A kind of biology base composite flame-retardant agent and its application Download PDF

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Publication number
CN109517188A
CN109517188A CN201811209677.0A CN201811209677A CN109517188A CN 109517188 A CN109517188 A CN 109517188A CN 201811209677 A CN201811209677 A CN 201811209677A CN 109517188 A CN109517188 A CN 109517188A
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lignin
flame
biology base
retardant
base composite
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刘鹏杰
孙峰
孙一峰
汪昭玮
岳小鹏
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Guangdong Institute Of Test And Analysis (guangzhou Analysis And Testing Center China)
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Guangdong Institute Of Test And Analysis (guangzhou Analysis And Testing Center China)
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/08—Oxygen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • 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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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Fireproofing Substances (AREA)

Abstract

The invention discloses a kind of biology base composite flame-retardant agent and its applications.A kind of biology base composite flame-retardant agent, is prepared by following steps: (1) lignin purification process: lignin purification process is obtained purifying lignin；(2) to purifying lignin phosphorylation modification；(3) biology base composite flame-retardant agent: the inorganic crystal whisker after drying is added in the phosphorylation lignin liquor of step (2) preparation, obtains biology base composite flame-retardant agent.Biology base composite flame-retardant agent proposed by the present invention, lignin after surface-modified has amphipathic, and modified lignin surface is negatively charged, dispersibility improves in the dry state for it, the boundary strength between lignin and inorganic crystal whisker and matrix is improved, to make biology base composite flame-retardant agent that there is more excellent comprehensive performance.

Description

A kind of biology base composite flame-retardant agent and its application
Technical field
The present invention relates to flame retardant area, in particular to a kind of biology base composite flame-retardant agent and its application.
Background technique
With the development of the social economy, all kinds of civilian, decorative composite material application field rapid expansions.Wherein, 90% or more composite material all has flammable properties, is shown according to 2017 annual datas, and the whole nation is informed of a case fire 21.9 ten thousand altogether, extremely 1065 people are died, severely injured 679 people cause 26.2 hundred million yuan of direct property loss.Wherein inflammable by composite material and initiation serious fire More than half of the China Zai Zhan fire total degree every year on average.Therefore, the demand of fire retardant and Flame-retardant composite material is can The future of prediction will be the indispensable important a part of marketing material demand class.
Fire retardant is divided into reactive flame retardant and additive flame retardant at present.However it commonly uses in the market and mature product master If realizing the fire-retardant purpose of product by being kneaded additive flame retardant.Additive flame retardant is divided into organic fire-retardant and nothing again Machine fire retardant, halogenated flame retardant (organic chloride and organic bromide) and non-halogen.It is organic be with bromine system, phosphorus nitrogen system, nitrogen system and Red phosphorus and compound are some fire retardants of representative, inorganic mainly antimony oxide, magnesium hydroxide, aluminium hydroxide, silicon systems etc. Flame-retardant system.
In addition to this, the increase with the mankind to the demand of the energy, energy crisis day are becoming tight, and white pollution is increasingly tight Weight, the mankind also gradually increase the consciousness of environmental protection and sustainable development.Therefore, environmentally friendly polymer composites It comes into being.However, current 90% or more polymer all has flammable properties, therefore the plant fiber for preparing flame retardant type is compound Material one of has become a hot topic of research.Aliphatic polyester (such as PLA, PBS, PBAT) is the high molecular material being commercialized, tool There are excellent biodegradable properties, is a kind of green syt resin.Inorfil has excellent intensity, toughness, source wide It is general, cheap, small advantage is worn to process equipment, it is compound in conjunction with being obtained after fire retardant and aliphatic polyester Material cladding Material has anti-flammability and biodegradable, while can substantially reduce the production cost of composite material.
Currently, novel, efficient, halogen-free flame retardants application has become the important development direction of fire-retardant scientific research, Halogen The research of fire retardant is concentrated mainly on three metal hydrate, red phosphorus and expansion type flame retardant (also referred to as Intumescent Retardant System) sides Face.Intumescent Retardant System generally refers to be mainly used in plastics row with phosphorus, nitrogen, the composite flame-retardant agent that carbon is main core component Secondly industry is the fields such as synthetic fibers, rubber, coating, paper and timber.
Existing fire retardant and flame-proof modifier are remarkably improved flame retardant property, but while flame retardant property improves, Along with the decline of mechanical property.Also, fire retardant is largely added so that the degradation property of composite material is remarkably decreased, in addition, Fire retardant majority does not have degradability, and the degradability of composite material can be destroyed by being added in aliphatic polyester.How So that fire retardant is had excellent anti-flammability, it is again biodegradable simultaneously, further, it is also possible to coordinate flame retardant properties, mechanical properties and Existing contradiction between degradation property while so that Flame Retardancy is improved, reduces fire retardant to material mechanical performance, degradation The influence of performance is the major issue that flame retardant area is faced.But presently relevant report is more deficient.
Summary of the invention
The present invention provides a kind of biology base composite flame-retardant agent and its application, by modifying agent it is modified to lignin surface at Inorganic crystal whisker is managed and adsorbs, modified lignin is provided with flame retardant property, and its hydrophobicity increases, in the polymer Degree of scatter increases, and plays humidification to matrix resin, meanwhile, make composite material that there is good flame retardant property, mechanical property Can, and its degradation property is influenced smaller.
To achieve the above object, The technical solution adopted by the invention is as follows:
A kind of biology base composite flame-retardant agent, is prepared by following steps:
(1) lignin purification process lignin purification process: is obtained into purifying lignin；
(2) to purifying lignin phosphorylation modification:
Firstly, compound concentration is the Na of 0.001~5g/mL2HPO4Solution, to Na2HPO4Epoxy chlorine is added dropwise in solution Propane (time for adding is 0.01~5h), the epoxychloropropane and Na2HPO4Mass ratio be 1/10~3/8, to epoxy chlorine Propane is added dropwise be heated to 30 DEG C~200 DEG C 0.01~10h of reaction after, it is cooling with ice-water bath after being cooled to room temperature, filter, and Residual solid deionized water is recrystallized 1~10 time, chloro- the third sodium phosphate of 2 hydroxyl of 3- is obtained；
Secondly, chloro- the third sodium phosphate of 2 hydroxyl of the 3- of above-mentioned preparation is adjusted pH to 7~14 with sodium hydroxide solution, 3- is obtained Chloro- the third sodium radio-phosphate,P-32 solution of 2 hydroxyl；
Finally, the purifying lignin that step (1) obtains is added into chloro- 2 hydroxyl, third sodium radio-phosphate,P-32 solution of 3-, and 0.01~10h is reacted at 30 DEG C~200 DEG C, obtains phosphorylation lignin liquor, the purifying lignin and Na2HPO4Matter Amount is than being 1.25~20:1；
(3) biology base composite flame-retardant agent: the phosphorylation lignin that step (2) preparation is added in the inorganic crystal whisker after drying is molten In liquid, 0.1~10h is stirred in water bath with thermostatic control, then is aged 0.1~10h in water bath with thermostatic control, and air blast is dry at 30 DEG C~200 DEG C It is dry to obtain biology base composite flame-retardant agent.
The present invention to lignin surface modification treatment and adsorbs inorganic crystal whisker by modifying agent, lignin tool after modified There is flame retardant property.Lignin after surface-modified has amphipathic, and modified lignin surface is negatively charged, Dispersibility improves under drying regime, the boundary strength between lignin and inorganic crystal whisker and matrix is improved, to make the biology Base composite flame-retardant agent has more excellent comprehensive performance, especially flame retardant property.
It is preferred that specific step is as follows for lignin purification process described in step (1): lignin is dissolved in dichloroethanes- In ethanol solution, the volume ratio of the dichloroethanes and ethyl alcohol is 1:1~10:1, after agitated standing centrifugation, takes centrifuge tube In supernatant be added anhydrous ether solution in stand centrifugation after, take centrifugation after solid be dried to obtain purifying lignin.
Further, it is wooden to be selected from alkali lignin, sulphur lignin, sodium lignosulfonate, ethyl alcohol for lignin described in step (1) One or more of element, acetone lignin, Milled wood lignin and enzyme lignin.
It is preferred that step (2) specifically includes the following steps:
Firstly, compound concentration is the Na of 0.1~0.5g/mL2HPO4Solution, to Na2HPO4Epoxy chlorine is added dropwise in solution Propane, the epoxychloropropane and Na2HPO4Mass ratio be 1/10~3/8, be added dropwise to epoxychloropropane and be heated to 30 DEG C~120 DEG C of 0.1~1h of reaction after, after cooling, suction filtration and crystallization treatment, obtain chloro- the third sodium phosphate of 2 hydroxyl of 3-；
Secondly, chloro- the third sodium phosphate of 2 hydroxyl of the 3- of above-mentioned preparation is adjusted pH to 8~12 with sodium hydroxide solution, 3- is obtained Chloro- the third sodium radio-phosphate,P-32 solution of 2 hydroxyl；
Finally, the purifying lignin that step (1) obtains is added into chloro- 2 hydroxyl, third sodium radio-phosphate,P-32 solution of 3-, and 0.1~5h is reacted at 40 DEG C~100 DEG C, obtains phosphorylation lignin liquor, the purifying lignin and Na2HPO4Quality Than for 1.25~20:1.
It is preferred that inorganic crystal whisker and Na after drying described in step (3)2HPO4Mass ratio be 0.125~1:1, it is described Inorganic crystal whisker be selected from alkali magnesium sulfate crystal whisker, magnesium hydroxide crystal whisker, aluminium hydroxide whisker, calcium carbonate crystal whisker and magnesium borate crystal whisker One or more of.
It is preferred that the drying specific steps of the inorganic crystal whisker after drying described in step (3) are as follows: by inorganic crystal whisker at 60 DEG C At~200 DEG C after dry 3~10h, it is cooled to room temperature to get the inorganic crystal whisker after the drying is arrived.
It is preferred that the specific steps of step (3) are as follows: the inorganic crystal whisker after drying is added to the phosphorylation wood of step (2) preparation In quality solution, 0.1~10h is stirred in 30 DEG C~80 DEG C of water bath with thermostatic control, then be aged in 30 DEG C~80 DEG C waters bath with thermostatic control 0.1~10h is dried to obtain biology base composite flame-retardant agent.
It is a further object to provide application of the above-mentioned biology base composite flame-retardant agent in Flame-retardant composite material.
Third object of the present invention is to provide a kind of Flame-retardant composite materials, are prepared by following steps: will dry Aliphatic polyester afterwards is added in the molding equipment that temperature is 80 DEG C~200 DEG C, and after aliphatic polyester melting, above-mentioned life is added The mass ratio of object base composite flame-retardant agent, the biology base composite flame-retardant agent and aliphatic polyester is 1/9~4/6, aliphatic poly Ester and biology base composite flame-retardant agent melt blending form to obtain Flame-retardant composite material.
It is preferred that the aliphatic polyester be selected from one of polylactic acid, pla-pcl and poly-succinic acid-butanediol rouge with On.
Compared with prior art, the invention has the following advantages that
1, inorganic crystal whisker is handled lignin and adsorbed by modifying agent, modified lignin is provided with flame retardant property, And its hydrophobicity increases, and degree of scatter in the polymer increases, and plays humidification to matrix resin, meanwhile, make multiple Condensation material have good flame retardant properties, mechanical properties, and on its degradation property influence it is smaller, it is low in cost, be conducive to batch, Continuously, the industrial production of scale.
2, the biology base composite flame-retardant agent of preparation method preparation through the invention can be used for a variety of degradable aliphatic adoptions Ester group body, Compound Machining performance is good, and raw material is restricted small, and the biology base composite flame-retardant agent products application is extensive, can be used in The fire proofings flame-retardant additives such as mechanical transport interior trim, communal facility, furniture item, building construction material, packaging.The biology base Composite flame-proof performance is excellent, lower production costs, for improve biomass material using it is horizontal, reduce fire, economize on resources, Protection environment and the property of society have great significance.
Detailed description of the invention
Fig. 1: the tensile strength and bending strength figure of anti-flammability composite material is made in Examples 1 to 7；
Fig. 2: UL-94 and the LOI figure of anti-flammability composite material is made in Examples 1 to 7.
Specific embodiment
The present invention will be further described in the following with reference to the drawings and specific embodiments.
A kind of preparation of anti-flammability composite material, comprising the following steps:
(1) lignin purification process: weighing suitable lignin raw material, be dissolved at room temperature volume ratio be 1:1~ The dichloroethanes of 10:1: in the solution of ethyl alcohol, stirring 1~60min, be centrifuged after standing in centrifuge, and centrifugal speed is 50~ 10000r/min.Then, supernatant in centrifuge tube is taken to be added in 0.01~2L anhydrous ether solution after precipitation to be precipitated.From Heart speed is that centrifuging and taking solid is dried in 20 DEG C~200 DEG C of vacuum oven in 50~10000r/min centrifuge, is obtained Purifying lignin is simultaneously spare.
(2) surface modifier is to purifying lignin phosphorylation modification:
Firstly, 10~500mL milliliters of deionized water and the Na of 5~100g are added in three-necked flask2HPO4·12H2O, Then, 1~60min of heating stirring in the water-bath that temperature is 5 DEG C~100 DEG C, is and then added dropwise in the above solution The epoxychloropropane (time for adding is 0.01~5h) of 0.5~100g, the heating reaction 0.01 in 30 DEG C~200 DEG C of oil bath pan After~10h, suction filtration cooling with ice-water bath after room temperature is continued cool to, and residual solid deionized water is recrystallized 1~10 It is secondary, obtain chloro- the third sodium phosphate of 2 hydroxyl of 3-.
Secondly, chloro- the third sodium phosphate of 2 hydroxyl of the 3- of above-mentioned preparation is adjusted into pH to 7~14 with a certain amount of sodium hydroxide solution, Obtain chloro- the third sodium radio-phosphate,P-32 solution of 2 hydroxyl of 3-.
Finally, again in chloro- the third sodium radio-phosphate,P-32 solution of 2 hydroxyl of 3- be added 1~500g purifying lignin, and 30 DEG C~ 0.01~10h is reacted at 200 DEG C, obtains phosphorylation lignin liquor.
(3) preparation of inorganic crystal whisker: weighing after inorganic crystal whisker is placed in the dry 3~10h of 60 DEG C~200 DEG C air dry ovens, It then cools to room temperature rear spare.
(4) prepared by biology base composite flame-retardant agent: the phosphorylation that the inorganic crystal whisker after drying is added to above-mentioned preparation is wooden In plain solution, 0.1~10h is stirred in 30 DEG C~100 DEG C of constant temperature of water-bath, then in 30 DEG C~100 DEG C of constant temperature of water-bath 0.1~10h is aged in pot, finally forced air drying obtains biology base composite flame-retardant agent at 30 DEG C~200 DEG C.
(5) preparation of Flame-retardant composite material:
Firstly, it is spare that aliphatic polyester is placed in the dry 6~12h of 60 DEG C~100 DEG C air dry ovens；
Secondly, aliphatic polyester is added in the molding equipment that temperature is 80 DEG C~200 DEG C, melted to aliphatic polyester Afterwards, then biology base composite flame-retardant agent obtained in step (4) is put into, melt blending forms to obtain composite material.
The mass ratio of biology base composite flame-retardant agent and aliphatic polyester is 1/9~4/6, and the mode of melt-processed is selected close One of refining/mill and hot-forming or extrusion molding.
Embodiment 1:
A kind of Flame-retardant composite material, is prepared by following steps:
(1) lignin purification process: weighing 200g lignin raw material, is dissolved in two that volume ratio is 1:1 at room temperature Chloroethanes: in the solution of ethyl alcohol, 10min is stirred, is centrifuged in centrifuge after standing, centrifugal speed 1000r/min.Then, Supernatant in centrifuge tube is taken to be added in 0.1L anhydrous ether solution after precipitation to be precipitated.Centrifugal speed be 1000r/min from Centrifuging and taking solid is dried in 50 DEG C of vacuum oven in scheming obtains purifying lignin and spare.
(2) surface modifier is to lignin phosphorylation modification:
Firstly, compound concentration is the Na of 0.5g/mL in three-necked flask2HPO4Solution, Na2HPO4Na in solution2HPO4's Quality is 5g.And then the epoxychloropropane (time for adding 1min) of 0.5g is added dropwise in the above solution, at 30 DEG C It in water-bath after heating reaction 0.1h, continues cool to cooling with ice-water bath after room temperature, filters, and by residual solid deionization Water recrystallizes 1 time, obtains chloro- the third sodium phosphate of 2 hydroxyl of 3-.
Secondly, chloro- the third sodium phosphate of 2 hydroxyl of the 3- of above-mentioned preparation is adjusted pH to 8 with a certain amount of sodium hydroxide solution, obtain Chloro- the third sodium radio-phosphate,P-32 solution of 2 hydroxyl of 3-.
Finally, the purifying lignin of 100g is added in chloro- the third sodium radio-phosphate,P-32 solution of 2 hydroxyl of 3-, and reacted at 40 DEG C 0.1h obtains phosphorylation lignin liquor.
(3) it the preparation of inorganic crystal whisker: weighs after calcium carbonate crystal whisker is placed in the dry 10h of 60 DEG C of air dry ovens, then cools down It is spare after to room temperature.
(4) prepared by biology base composite flame-retardant agent:
Inorganic crystal whisker 5g after will be dry in step (3) is added in the phosphorylation lignin liquor of step (2) preparation, 0.1h is stirred in the water-bath that 30 DEG C of constant temperature, is then aged 0.1h in 30 DEG C of constant temperature of water-bath, finally the air blast at 50 DEG C It is dried to obtain biology base composite flame-retardant agent.
(5) preparation of Flame-retardant composite material:
After poly butylene succinate (PBS) is placed in the dry 8h of 80 DEG C of air dry ovens, by following mass percent Match material: biology base composite flame-retardant agent 10%, PBS 90%.Mill mixing 15min, hot-forming under the conditions of 110 DEG C, system It is standby to obtain degradable PBS Flame-retardant composite material.
Gained PBS Flame-retardant composite material performance is shown in Fig. 1 and Fig. 2 after tested.
Embodiment 2:
A kind of Flame-retardant composite material, is prepared by following steps:
(1) lignin purification process: weighing 200g lignin raw material, is dissolved in two that volume ratio is 2:1 at room temperature Chloroethanes: in the solution of ethyl alcohol, 10min is stirred, is centrifuged in centrifuge after standing, centrifugal speed 1000r/min.Then, Supernatant in centrifuge tube is taken to be added in 0.1L anhydrous ether solution after precipitation to be precipitated.Centrifugal speed be 1000r/min from Centrifuging and taking solid is dried in 50 DEG C of vacuum oven in scheming obtains purifying lignin and spare.
(2) surface modifier is to lignin phosphorylation modification:
Firstly, compound concentration is the Na of 0.1g/mL in three-necked flask2HPO4Solution, Na2HPO4Na in solution2HPO4's Quality is 10g.And then in Na2HPO4The epoxychloropropane (time for adding 5min) of 1g is added dropwise in solution, at 80 DEG C It in water-bath after heating reaction 0.5h, continues cool to cooling with ice-water bath after room temperature, filters, and by residual solid deionization Water recrystallizes 1 time, obtains chloro- the third sodium phosphate of 2 hydroxyl of 3-.
Secondly, chloro- the third sodium phosphate of 2 hydroxyl of the 3- of above-mentioned preparation is adjusted pH to 8 with a certain amount of sodium hydroxide solution, obtain Chloro- the third sodium radio-phosphate,P-32 solution of 2 hydroxyl of 3-.
Finally, the purifying lignin of 200g is added in chloro- the third sodium radio-phosphate,P-32 solution of 2 hydroxyl of 3- again, and reacted at 50 DEG C 0.5h obtains phosphorylation lignin liquor.
(3) preparation of inorganic crystal whisker: weighing after magnesium hydroxide crystal whisker is placed in the dry 10h of 60 DEG C of air dry ovens, then cold But to spare after room temperature.
(4) prepared by biology base composite flame-retardant agent: the inorganic crystal whisker 10g of step (3) after dry is added to step (2) preparation Phosphorylation lignin liquor in, stir 0.5h in 50 DEG C of constant temperature of water-bath, it is then old in 50 DEG C of constant temperature of water-bath Change 0.5h, finally forced air drying obtains biology base composite flame-retardant agent at a temperature of 60 DEG C.
(5) preparation of Flame-retardant composite material: after polylactic acid (PLA) is placed in the dry 8h of 80 DEG C of air dry ovens, by such as Under mass percent match material: biology base composite flame-retardant agent 20%, PLA 80%.Mill mixing under the conditions of 160 DEG C 15min, it is hot-forming, degradable PLA Flame-retardant composite material is prepared.
The PLA Flame-retardant composite material performance in gained embodiment 2 is shown in Fig. 1 and Fig. 2 after tested.
Embodiment 3:
A kind of Flame-retardant composite material, is prepared by following steps:
(1) lignin purification process: weighing 100g lignin raw material, is dissolved in two that volume ratio is 10:1 at room temperature Chloroethanes: in the solution of ethyl alcohol, 60min is stirred, is centrifuged in centrifuge after standing, centrifugal speed 10000r/min.Then, Supernatant in centrifuge tube is taken to be added in 2L anhydrous ether solution after precipitation to be precipitated.It is 10000r/min centrifugation in centrifugal speed Centrifuging and taking solid is dried in 150 DEG C of vacuum oven in machine obtains purifying lignin and spare.
(2) surface modifier is to lignin phosphorylation modification:
Firstly, compound concentration is the Na of 0.16g/mL in three-necked flask2HPO4Solution, Na2HPO4Na in solution2HPO4's Quality is 80g.And then in Na2HPO4The epoxychloropropane (time for adding 30min) of 30g is added dropwise in solution, 120 DEG C oil bath pan in after heating reaction 1h, continue cool to cooling with ice-water bath after room temperature, filter, and by residual solid spend from Sub- water recrystallizes 10 times, obtains chloro- the third sodium phosphate of 2 hydroxyl of 3-.
Secondly, chloro- the third sodium phosphate of 2 hydroxyl of the 3- of above-mentioned preparation is adjusted pH to 12 with a certain amount of sodium hydroxide solution, obtain To chloro- the third sodium radio-phosphate,P-32 solution of 2 hydroxyl of 3-.
Finally, the purifying lignin of 100g is added in chloro- the third sodium radio-phosphate,P-32 solution of 2 hydroxyl of 3- again, and reacted at 100 DEG C 5h obtains phosphorylation lignin liquor.
(3) preparation of inorganic crystal whisker: weighing after aluminium hydroxide whisker is placed in the dry 10h of 80 DEG C of air dry ovens, then cold But to spare after room temperature.
(4) prepared by biology base composite flame-retardant agent: the inorganic crystal whisker 10g of step (3) after dry is added to step (2) preparation Phosphorylation lignin liquor in, stir 10h in 80 DEG C of constant temperature of water-bath, be then aged in 80 DEG C of constant temperature of water-bath 10h, finally forced air drying obtains biology base composite flame-retardant agent at 80 DEG C.
(5) preparation of Flame-retardant composite material: after PBS is placed in the dry 12h of 100 DEG C of air dry ovens, by following matter It measures percentage and matches material: biology base composite flame-retardant agent 40%, PBS 60%.Mill mixing 15min under the conditions of 120 DEG C, heat It is molded, degradable PBS Flame-retardant composite material is prepared.
The PBS Flame-retardant composite material performance in gained embodiment 3 is shown in Fig. 1 and Fig. 2 after tested.
Embodiment 4:
A kind of Flame-retardant composite material, is prepared by following steps:
(1) lignin purification process: weighing 100g lignin raw material, is dissolved in two that volume ratio is 10:1 at room temperature Chloroethanes: in the solution of ethyl alcohol, 60min is stirred, is centrifuged in centrifuge after standing, centrifugal speed 10000r/min.Then, Supernatant in centrifuge tube is taken to be added in 2L anhydrous ether solution after precipitation to be precipitated.It is 10000r/min centrifugation in centrifugal speed Centrifuging and taking solid is dried in 150 DEG C of vacuum oven in machine obtains purifying lignin and spare.
(2) surface modifier is to lignin phosphorylation modification:
Firstly, compound concentration is the Na of 0.16g/mL in three-necked flask2HPO4Solution, Na2HPO4Na in solution2HPO4's Quality is 80g.And then the epoxychloropropane (time for adding 30min) of 30g is added dropwise in the above solution, at 120 DEG C Oil bath pan in after heating reaction 1h, continue cool to cooling with ice-water bath after room temperature, filter, and by residual solid deionization Water recrystallizes 10 times, obtains chloro- the third sodium phosphate of 2 hydroxyl of 3-.
Secondly, with a certain amount of sodium hydroxide solution by chloro- the third sodium radio-phosphate,P-32 solution of 2 hydroxyl of the 3- of above-mentioned preparation adjust pH to 12, obtain chloro- the third sodium radio-phosphate,P-32 solution of 2 hydroxyl of 3-.
Finally, the purifying lignin of 100g is added in chloro- the third sodium radio-phosphate,P-32 solution of 2 hydroxyl of 3- again, and reacted at 100 DEG C 5h obtains phosphorylation lignin liquor.
(3) it the preparation of inorganic crystal whisker: weighs after alkali magnesium sulfate crystal whisker is placed in the dry 10h of 80 DEG C of air dry ovens, then It is cooled to room temperature rear spare.
(4) prepared by biology base composite flame-retardant agent: the inorganic crystal whisker 10g of step (3) after dry is added to step (2) preparation Phosphorylation lignin liquor in, stir 10h in 80 DEG C of constant temperature of water-bath, be then aged in 80 DEG C of constant temperature of water-bath 10h, finally forced air drying obtains biology base composite flame-retardant agent at 80 DEG C.
(5) preparation of Flame-retardant composite material: after PLA/PBS is placed in the dry 12h of 100 DEG C of air dry ovens, by as follows Mass percent match material: biology base composite flame-retardant agent 30%, PLA/PBS (the mass ratio 1:1 of PLA and PBS) 70%. Mill mixing 15min, hot-forming under the conditions of 170 DEG C, and degradable PLA/PBS Flame-retardant composite material is prepared.
The PLA/PBS Flame-retardant composite material performance in gained embodiment 4 is shown in Fig. 1 and Fig. 2 after tested.
Embodiment 5 (comparative example 1)
A kind of Flame-retardant composite material, is prepared by following steps:
(1) lignin purification process: weighing 100g lignin raw material, is dissolved in two that volume ratio is 10:1 at room temperature Chloroethanes: in the solution of ethyl alcohol, 60min is stirred, is centrifuged in centrifuge after standing, centrifugal speed 10000r/min.Then, Supernatant in centrifuge tube is taken to be added in 2L anhydrous ether solution after precipitation to be precipitated.It is 10000r/min centrifugation in centrifugal speed Centrifuging and taking solid is dried in 150 DEG C of vacuum oven in machine obtains purifying lignin and spare.
(2) surface modifier is to lignin phosphorylation modification:
Firstly, compound concentration is the Na of 0.16g/mL in three-necked flask2HPO4Solution, Na2HPO4Na in solution2HPO4's Quality is 80g.And then the epoxychloropropane (time for adding 30min) of 30g is added dropwise in the above solution, at 120 DEG C Oil bath pan in after heating reaction 1h, continue cool to cooling with ice-water bath after room temperature, filter, and by residual solid deionization Water recrystallizes 10 times, obtains chloro- the third sodium phosphate of 2 hydroxyl of 3-.
Secondly, with a certain amount of sodium hydroxide solution by chloro- the third sodium radio-phosphate,P-32 solution of 2 hydroxyl of the 3- of above-mentioned preparation adjust pH to 12, obtain chloro- the third sodium radio-phosphate,P-32 solution of 2 hydroxyl of 3-.
Finally, the purifying lignin of 100g is added in chloro- the third sodium radio-phosphate,P-32 solution of 2 hydroxyl of 3- again, and reacted at 100 DEG C 5h obtains phosphorylation lignin liquor.
(3) prepared by biology base composite flame-retardant agent: by the phosphorylation lignin liquor of step (2) preparation, air blast is dry at 80 DEG C It is dry to obtain biological based flameproofing.
(4) preparation of Flame-retardant composite material: after PLA/PBS is placed in the dry 12h of 100 DEG C of air dry ovens, by as follows Mass percent match material: biological based flameproofing 30%, PLA/PBS (the mass ratio 1:1 of PLA and PBS) 70%.170℃ Under the conditions of mill mixing 15min, it is hot-forming, degradable PLA/PBS Flame-retardant composite material is prepared.
The PLA/PBS Flame-retardant composite material performance in gained embodiment 5 is shown in Fig. 1 and Fig. 2 after tested.
Embodiment 6 (comparative example 2)
A kind of Flame-retardant composite material, is prepared by following steps:
(1) it the preparation of inorganic crystal whisker: weighs after alkali magnesium sulfate crystal whisker is placed in the dry 10h of 80 DEG C of air dry ovens, then It is cooled to room temperature rear spare.
(2) preparation of Flame-retardant composite material: after PLA/PBS is placed in the dry 12h of 100 DEG C of air dry ovens, by as follows Mass percent match material: alkali magnesium sulfate crystal whisker 30%, PLA/PBS (the mass ratio 1:1 of PLA and PBS) 70%.170 Mill mixing 15min under the conditions of DEG C, it is hot-forming, degradable PLA/PBS Flame-retardant composite material is prepared.
The PLA/PBS Flame-retardant composite material performance in gained embodiment 6 is shown in Fig. 1 and Fig. 2 after tested.
Embodiment 7:
It is same as Example 4, the difference is that: aliphatic polyester is pla-pcl.
A kind of Flame-retardant composite material, is prepared by following steps:
(1) lignin purification process: weighing 100g lignin raw material, is dissolved in two that volume ratio is 10:1 at room temperature Chloroethanes: in the solution of ethyl alcohol, 60min is stirred, is centrifuged in centrifuge after standing, centrifugal speed 10000r/min.Then, Supernatant in centrifuge tube is taken to be added in 2L anhydrous ether solution after precipitation to be precipitated.It is 10000r/min centrifugation in centrifugal speed Centrifuging and taking solid is dried in 150 DEG C of vacuum oven in machine obtains purifying lignin and spare.
(2) surface modifier is to lignin phosphorylation modification:
Firstly, compound concentration is the Na of 0.16g/mL in three-necked flask2HPO4Solution, Na2HPO4Na in solution2HPO4's Quality is 80g.And then the epoxychloropropane (time for adding 30min) of 30g is added dropwise in the above solution, at 120 DEG C Oil bath pan in after heating reaction 1h, continue cool to cooling with ice-water bath after room temperature, filter, and by residual solid deionization Water recrystallizes 10 times, obtains chloro- the third sodium phosphate of 2 hydroxyl of 3-.
Secondly, with a certain amount of sodium hydroxide solution by chloro- the third sodium radio-phosphate,P-32 solution of 2 hydroxyl of the 3- of above-mentioned preparation adjust pH to 12, obtain chloro- the third sodium radio-phosphate,P-32 solution of 2 hydroxyl of 3-.
Finally, the purifying lignin of 100g is added in chloro- the third sodium radio-phosphate,P-32 solution of 2 hydroxyl of 3- again, and reacted at 100 DEG C 5h obtains phosphorylation lignin liquor.
(3) it the preparation of inorganic crystal whisker: weighs after calcium carbonate crystal whisker is placed in the dry 10h of 80 DEG C of air dry ovens, then cools down It is spare after to room temperature.
(4) prepared by biology base composite flame-retardant agent: the inorganic crystal whisker 10g of step (3) after dry is added to step (2) preparation Phosphorylation lignin liquor in, stir 10h in 80 DEG C of constant temperature of water-bath, be then aged in 80 DEG C of constant temperature of water-bath 10h, finally forced air drying obtains biology base composite flame-retardant agent at 80 DEG C.
(5) it the preparation of Flame-retardant composite material: after pla-pcl (PCL) is placed in the dry 12h of 50 DEG C of air dry ovens, presses Following mass percent matches material: biology base composite flame-retardant agent 30%, PCL 70%.Mill mixing under the conditions of 80 DEG C 15min, it is hot-forming, degradable PCL Flame-retardant composite material is prepared.
The PCL Flame-retardant composite material performance in gained embodiment 7 is shown in Fig. 1 and Fig. 2 after tested.
As shown in Figure 1 and Figure 2, the mechanical property of the composite material of different matrix composite material after adding different fire retardants Energy and flame retardant property are all changed.Compared to other embodiments, the LOI value for the PBS Flame-retardant composite material that embodiment 3 obtains Highest, but since excessive fire retardant makes the mechanical properties decrease of composite material.In addition, in matrix and fire retardant additive amount phase With under conditions of, embodiment 5 and embodiment 6, the PLA/PBS that the embodiment 4 prepared by biology base composite flame-retardant agent obtains are compared Its tensile strength of Flame-retardant composite material and bending strength are highest, and its oxygen index (OI) is 32.1% (oxygen index (OI) > 27.0% is nonflammable material), UL-94 has also reached V-0 grades.Its mechanical property meets actual production with flame retardant property simultaneously to be made With requiring.This explanation compares single fire retardant, and biology base composite flame-retardant agent has synergistic enhancing resistance to Flame-retardant composite material The effect of combustion.Which solve flame retardant type plastic product, flame retardant property and mechanical property cannot meet use simultaneously in actual production Contradiction.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention etc. It should be equivalent substitute mode, be included within the scope of the present invention.

Claims (10)

1. a kind of biology base composite flame-retardant agent, which is characterized in that be prepared by following steps:
(1) lignin purification process lignin purification process: is obtained into purifying lignin；
(2) to purifying lignin phosphorylation modification:
Firstly, compound concentration is the Na of 0.001~5g/mL2HPO4Solution, to Na2HPO4Epoxychloropropane is added dropwise in solution, The epoxychloropropane and Na2HPO4Mass ratio be 1/10~3/8, be added dropwise to epoxychloropropane be heated to 30 DEG C~ After 200 DEG C of 0.01~10h of reaction, after cooling, suction filtration and crystallization treatment, chloro- the third sodium phosphate of 2 hydroxyl of 3- is obtained；
Secondly, chloro- the third sodium phosphate of 2 hydroxyl of the 3- of above-mentioned preparation is adjusted pH to 7~14 with sodium hydroxide solution, 3- chloro- 2 is obtained The third sodium radio-phosphate,P-32 solution of hydroxyl；
Finally, the purifying lignin that step (1) obtains is added into chloro- 2 hydroxyl, third sodium radio-phosphate,P-32 solution of 3-, and at 30 DEG C 0.01~10h is reacted at~200 DEG C, obtains phosphorylation lignin liquor, the purifying lignin and Na2HPO4Mass ratio For 1.25~20:1；
(3) inorganic crystal whisker after drying biology base composite flame-retardant agent: is added to the phosphorylation lignin liquor of step (2) preparation In, 0.1~10h is stirred in water bath with thermostatic control, then 0.1~10h is aged in water bath with thermostatic control, be dried to obtain biology base composite flame-proof Agent.
2. biology base composite flame-retardant agent as described in claim 1, which is characterized in that at lignin purifying described in step (1) Specific step is as follows for reason: lignin being dissolved in dichloro-ethane-ethanol solution, the volume ratio of the dichloroethanes and ethyl alcohol For 1:1~10:1, after agitated standing centrifugation, the supernatant in centrifuge tube is taken to be added in anhydrous ether solution after standing centrifugation, Solid after taking centrifugation is dried to obtain purifying lignin.
3. biology base composite flame-retardant agent as claimed in claim 2, which is characterized in that lignin described in step (1) is selected from One of alkali lignin, sulphur lignin, sodium lignosulfonate, ethyl alcohol lignin, acetone lignin, Milled wood lignin and enzyme lignin with On.
4. biology base composite flame-retardant agent as described in claim 1, which is characterized in that step (2) specifically includes the following steps:
Firstly, compound concentration is the Na of 0.1~0.5g/mL2HPO4Solution, to Na2HPO4Epoxychloropropane is added dropwise in solution, The epoxychloropropane and Na2HPO4Mass ratio be 1/10~3/8, be added dropwise to epoxychloropropane be heated to 30 DEG C~ After 120 DEG C of 0.1~1h of reaction, after cooling, suction filtration and crystallization treatment, chloro- the third sodium phosphate of 2 hydroxyl of 3- is obtained；
Secondly, chloro- the third sodium phosphate of 2 hydroxyl of the 3- of above-mentioned preparation is adjusted pH to 8~12 with sodium hydroxide solution, 3- chloro- 2 is obtained The third sodium radio-phosphate,P-32 solution of hydroxyl；
Finally, the purifying lignin that step (1) obtains is added into chloro- 2 hydroxyl, third sodium radio-phosphate,P-32 solution of 3-, and at 40 DEG C 0.1~5h is reacted at~100 DEG C, obtains phosphorylation lignin liquor, the purifying lignin and Na2HPO4Mass ratio be 1.25~20:1.
5. biology base composite flame-retardant agent as described in claim 1, which is characterized in that the nothing after drying described in step (3) Machine whisker and Na2HPO4Mass ratio be 0.125~1:1, the inorganic crystal whisker be selected from alkali magnesium sulfate crystal whisker, magnesium hydroxide One or more of whisker, aluminium hydroxide whisker, calcium carbonate crystal whisker and magnesium borate crystal whisker.
6. biology base composite flame-retardant agent as claimed in claim 1 or 5, which is characterized in that after drying described in step (3) The drying specific steps of inorganic crystal whisker are as follows: after dry 3~10h, be cooled to room temperature inorganic crystal whisker, i.e., at 60 DEG C~200 DEG C Inorganic crystal whisker after obtaining the drying.
7. biology base composite flame-retardant agent as described in claim 1, which is characterized in that the specific steps of step (3) are as follows: will dry Inorganic crystal whisker afterwards is added in the phosphorylation lignin liquor of step (2) preparation, stirs in 30 DEG C~80 DEG C of water bath with thermostatic control 0.1~10h, then 0.1~10h is aged in 30 DEG C~80 DEG C waters bath with thermostatic control, it is dried to obtain biology base composite flame-retardant agent.
8. application of the biology base composite flame-retardant agent described in claim 1 in Flame-retardant composite material.
9. a kind of Flame-retardant composite material, which is characterized in that be prepared by following steps: the aliphatic polyester after drying is added Enter in the molding equipment that temperature is 80 DEG C~200 DEG C, after aliphatic polyester melting, biology base described in claim 1 is added The mass ratio of composite flame-retardant agent, the biology base composite flame-retardant agent and aliphatic polyester be 1/9~4/6, aliphatic polyester and Biology base composite flame-retardant agent melt blending forms to obtain Flame-retardant composite material.
10. Flame-retardant composite material as claimed in claim 9, which is characterized in that the aliphatic polyester be selected from polylactic acid, One or more of pla-pcl and poly-succinic acid-butanediol rouge.
CN201811209677.0A 2018-10-17 2018-10-17 A kind of biology base composite flame-retardant agent and its application Pending CN109517188A (en)

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Application publication date: 20190326