CN101348553A - Plant polyatomic alcohol polyurethane rigid foam material - Google Patents
Plant polyatomic alcohol polyurethane rigid foam material Download PDFInfo
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Abstract
A plant polyol polyurethane rigid foam relates to a polyurethane material. The plant polyol polyurethane rigid foam is characterized in that: firstly crushing weed wood and bamboo are screened over an 80-mesh sieve; then according to a weight ratio, 700 to 800kg of mixed powder, 350 to 400kg of carbowax, 18.7 to 19kg of diethylene glycol, 70 to 80kg of glycerol (for medical use), 5.5 to 6kg of a plant activator, 20 to 40kg of a biological degradation ester, and 80 to 120kg of plant powder are added into a reaction kettle for liquefaction to produce a plant polyol which replaces 2/3 of polyether to constitute a foam base material; the foam base material is mixed and reacted with a catalyst, water and an isocyanic acid to form the polyurethane rigid foam. The polyurethane rigid foam has the advantages that: the plant weed wood used as the raw material is crushed and liquefied to produce the plant polyol which replaces 2/3 of the raw material to produce polyurethane foamed plastics. The plant polyol polyurethane rigid foam realizes the replacement of the petrochemical material of propylene oxide, thereby not only saving petroleum material, but also realizing weed wood utilization, simultaneously reaching the environmental protection requirements on degradability and making the high-standard degradable polyurethane have wider applications.
Description
Technical field:
The present invention relates to polyurethane material
Background technology:
Urethane (polyurethanes) material is the present best lagging material of performance in the world.Main chain contains-base polymer of NHCOO-repeated structural unit.English abbreviation PU.Urethane has easy foaming, can regulate the soft or hard degree, and goods are attractive in appearance, and therefore advantages such as handling ease have become one of the world's six big synthesized polymer materials.Be widely used in fiber, light industry, material of construction, industry such as wrapping material and automobile.The raw material of urethane mainly came from petrochemical complex in the past, consumed a large amount of valuable petroleum resources, and goods are difficult to decompose and recycling after discarded, had caused serious pollution problem.Exploitation has become one of more and more urgent problem based on renewable resources and degradable polyurethane material.
On the other hand, as preferred fast growing wood kind, under the wideling popularize of Ministry of Forestry, China fir is extensively planted at southern china.Seldom obtain utilizing in the pulping and paper-making industry owing to the thin weak point of its kind trunk fiber, its soft wood performance has also limited its application at other field in addition.
Summary of the invention:
The objective of the invention is to utilize the component of weedtree, a kind of degradable plant polyatomic alcohol polyurethane rigid foam material is provided as urethane.
The solution of the present invention is:
1) weedtree, mao bamboon are put into the drying machine drying
2) putting into pulverizer by weedtree and mao bamboon weight ratio 4: 1～0.8 proportioning pulverizes;
3) the crushed mixed powder material is filtered out powder mix below the 80 purpose fineness through sieve shaker;
4) by weight with powder mix 700～800kg, polyoxyethylene glycol 350～400kg, glycol ether 18.7～19kg, glycerine (medical grade) 70～80kg, plant activator 5.5～6kg, biological degradation ester 20～40kg, plant powder 80～120kg feeds intake and liquefies to reactor, produces plant polyatomic alcohol;
5) by weight plant polyatomic alcohol 35～40kg, polyethers 20～25kg, polyester 15～20kg, whipping agent 141b18kg, varies catalyzer 2.3kg, silicone oil 1.5～2kg, linking agent 6～7kg, water 0.5kg, PZA (six hydrogen, three dais) 0.5～1kg, tensio-active agent 2～3kg uniform mixing are formed the foaming base-material;
6) will foam base-material and isocyanic ester PAPI by weight 1: 1.2～1.3 and catalyzer, water inject respectively that cavity hybrid reaction forms hard polyurethane foam in spray gun or the injection moulding machine.
The invention has the advantages that:
With the plant weedtree is that raw material is pulverized, liquefying is made into plant polyatomic alcohol, substitutes 2/3 starting material with plant polyatomic alcohol and makes urethane foam.Realized the replacement of petrochemical materials epoxy third, not only saved petroleum, and realized that the weedtree utilization reaches the degradable environmental requirement simultaneously, makes high standard degradable polyurethane purposes more extensive.
Description of drawings:
Fig. 1 is the preceding microvoid structure of degraded.
Fig. 2 begins to become the large micropore structure for network space in the degraded
Fig. 3 progressively becomes the large micropore structure for network space in the degraded
Fig. 4 is micropore mycelia or bacterium colony figure.
Embodiment:
Making step of the present invention is:
1) weedtree, mao bamboon are put into the drying machine drying
2) putting into pulverizer by weedtree and mao bamboon weight ratio 4: 1～0.8 proportioning pulverizes;
3) the crushed mixed powder material is filtered out powder mix below the 80 purpose fineness through sieve shaker;
4) by weight with powder mix 700～800kg, polyoxyethylene glycol 350～400kg, glycol ether 18.7～19kg, glycerine (medical grade) 70～80kg, plant activator 5.5～6kg, biological degradation ester 20～40kg, plant powder 80～120kg feeds intake and liquefies to reactor, produces plant polyatomic alcohol;
5) by weight plant polyatomic alcohol 35～40kg, polyethers 20～25kg, polyester 15～20kg, whipping agent 141b18kg, varies catalyzer 2.3kg, silicone oil 1.5～2kg, linking agent 6～7kg, water 0.5kg, PZA (six hydrogen, three dais) 0.5～1kg, tensio-active agent 2～3kg uniform mixing are formed the foaming base-material;
6) will foam base-material and isocyanic ester PAPI by weight 1: 1.2～1.3 and catalyzer, water inject respectively that cavity hybrid reaction forms hard polyurethane foam in spray gun or the injection moulding machine
Below with regard to experimental technique, plant polyatomic alcohol preparation technology, analysis of experiments, pilot process condition describe in detail:
One, experimental technique
The selection of 1-1 plant material
Different its character in the place of production of considering China fir limit vegetable fibre are difference to some extent, therefore we at first research and develop the China fir mock in Fujian Province, and find that in experiment vegetable fibre has comparatively significantly effect to the decline of material monolithic density, but in the industrial powder of China fir, add mao bamboon and just can make the requirement of wood powder powder essence to 80 purpose. (according to local circumstances: only in the China fir powder, add the mao bamboon powder and just can make wood powder powder essence to 80 order. therefore on the liquefaction basis of China fir powder, carried out compound (the China fir powder:, mao bamboon powder=8: 2) liquefaction research. owing to the reasons such as market supply variation of considering plant material, also selected mixing wood powder (80 order) raw material of Zhejiang balcony to carry out the preparation research of polyvalent alcohol in addition. the composition analysis of above plant material the results are shown in table 1
Table 1 China fir mock utmost point weedtree, the chemical composition analysis result of mao bamboon powder and mixing wood powder
China fir powder mao bamboon powder mixing wood powder
Mierocrystalline cellulose (%) 42 26 45
Hemicellulose (%) 27 32 23
Xylogen (%) 28 24 25
Other (%) 3 18 7
At occurring in nature, there is the natural discarded plant raw material of a lot of rich cellulose.And Mierocrystalline cellulose self can not fusion, does not have thermoplasticity, and need carry out after the chemical modifications such as esterification, etherificate could machine-shaping, but modifying process can produce environmental pollution inevitably.Therefore this project adopts compound liquifying method above-mentioned that it is liquefied, and has obtained ideal results.
Technical division of company has carried out liquefaction research to the fiber of natural plant raw material China fir and mao bamboon.These two kinds of Mierocrystalline celluloses contain two kinds of fibers that the polymerization degree is different, but because the composition of mao bamboon is comparatively complicated.Employing is the compound liquifying method of catalyzer with sulfuric acid, with PEG and DEG is liquefied reagent, under condition of normal pressure, the solid fiber is liquefied as the polynary alcohol of aqueous Mierocrystalline cellulose, after alcoholysis and hydrolysis, its hydroxyl value can satisfy semi-rigid or synthetic require (4.5-10.7mmol/g) of hard polyaminoester
The chemical reagent that uses in this research is as follows:
Synthesizing polyether glycol: propylene oxide PPO, SU450L, technical pure
Urethane: poly-hexanodioic acid second diester, benzoic anhydride polyester polyol
Synthesis of polyurethane:
Vulcabond (TDI.MDI) technical pure
Triethylenediamine (TEDA) chemical pure
The silicone oil technical pure
Dibutyl tin laurate (DBTD) analytical pure
The plant activating enzymes
Synthesizing of 1-2 biological degradation aliphatic polyester
The polyvalent alcohol of preparation urethane is divided into polyether-type and polyester type usually. because the urethane that PAUR (particularly aliphatic polyester) makes has biodegradability preferably, usually easily by multiple microbiological deterioration.Therefore we carry out esterification modification with binary hydroxy acids such as DL-lactic acid, Succinic Acid, hexanodioic acid and certain herbaceous plants with big flowers diacid to PEG400 by the method for direct condensation, have finally obtained having the polyether glycol of terminal hydroxy group.With water is whipping agent, and under the catalysis of amine and tin class catalyzer, (MDI, TDI) reaction can obtain this foam of hard foamed poly urethane material for above-mentioned polyester ether polylol and isocyanic ester.Material all is better than pure PEG400 polyether ester on structure and performance.This class material can hydrolysis in hot water, and wherein the mass loss speed of urethane foam in hydrolytic process that makes with the TDI foaming of dibasic alcohol/PEG400 Succinic Acid modified PE G400 polyester ether polylol is greater than the urethane foam that makes with the MDI foaming.
Select poly-hexanodioic acid second diester that the mao bamboon powder is liquefied, react the mao bamboon powder polyurethane foamed material that makes with MDI then, has biological degradability preferably, but because the not clear composition of mao bamboon powder is more, therefore, its tear strength is not as pure wood powder PU in the PU structure, but its external cladding material that can be used as release controlled fertilizer etc. has biodegradability, therefore can discharge last about 30% residual quantity that can't discharge of general coating chemical fertilizer. adopt the biological degradation type polyurethane as coating, this part chemical fertilizer also is released. therefore, we need only the mao bamboon composition that draws readily biodegradable therein, just can obtain better slowly-releasing control effect.
The preparation of the poly-hexanodioic acid second diester of 1-2-1
In exsiccant 250ml three-necked bottle; add the 100g adipic acid crystals; a small amount of tosic acid (about 0.5g); 38.2ml ethylene glycol; 5ml dimethylbenzene; load onto agitator; nitrogen ingress pipe; arm separating funnel and prolong; under nitrogen protection; with oil bath heat temperature raising to 100 ℃, be warmed up to 120 ℃ through 1 hour again, have large quantity of moisture to steam this moment. add dimethylbenzene from the condensation mouth of pipe; make liquid level a little less than a mouth of pipe; slowly at 2 hours internal heating to 140 ℃, be warmed up to 155 ℃ again through 2 hours. in reaction system, add 0.5ml ethylene glycol, continue reaction 2 hours. then emit the water in the separating funnel; it is very little until the speed that water steams to keep this temperature. under nitrogen protection, be cooled to about 50 ℃; with product impouring beaker, this moment, product was slightly yellowy thick liquid. beaker is put into moisture eliminator continue cooling, can obtain white blocks of solid next day.
The mensuration of the poly-hexanodioic acid second diester acid number of 1-2-2
With the accurately poly-hexanodioic acid ethyl ester dissolving of weighing of pyridine, add several phenolphthalein indicators again, using, concentration is its acid number of NaOH solution titration of the demarcation of 1mol/l.
Acid number=56.1 * V (NaOH solution body product) * M (NaOH concentration)/W (sample quality)
The mensuration of the poly-hexanodioic acid second diester hydroxyl value of 1-2-3
Earlier the 17.9ml acetic anhydride is dissolved in the 200ml pyridine, is made into acylating agent and places brown bottle to use.Get a dry 25ml round-bottomed flask, accurately after the weighing, add about 3g synthetic polyethylene glycol adipate, move into the 10ml acylating agent, bottleneck is used the grinding port plug jam-pack after using pyridine drip washing, places 24 hours.Next day, with pyridine drip washing grinding port plug and bottleneck, put into several zeolites, connect through exsiccant air set pipe, reflux 1 hour.Be cooled to room temperature, with the liquid impouring Erlenmeyer flask in the bottle.In Erlenmeyer flask, add several phenolphthalein reagents, with the titration of proven standard 1mol/iNaOH solution.Do a blank reference experiment simultaneously, calculate hydroxyl value by following formula:
Hydroxyl value=56.1 * (blank sample consumption NaOH volume-sample consumption NaOH volume) * NaOH solution volumetric molar concentration/sample quality
Proofread and correct the hydroxyl value=acid number of surveying+actual measurement hydroxyl value
Determining of the mensuration of 1-3 plant material hydroxyl value and isocyanic ester consumption
The mensuration of hydroxyl value is referring to 1-4 in polyethers and the plant, and the consumption of isocyanic ester can carry out general estimation by following formula in the PU foam:
WMDI＝(WBK×HBK+WSU×HSU)×10-3×WNCO/PNCO+(WW×HW×2×10-3×WNCO/PNCO)
This formula is for the OH base value being the consumption of benchmark calculating MDI, be that NCO/OH is that (this ratio did not contain the OH value with the NCO and the water of water effect in 1: 1, every molNCO when therefore water and NCO react, generate 1molCO2), after the calculating, multiply by coefficient 1.1 by this calculated value, in order to system in the water of error part and the reaction of unknown hydroxyl.WMDI, WBK, hydroxyl value (mmOl/g) HW that application weight (g) HBK.HSU that WSU, WW are respectively MDI, plant material, polyethers SU450L is respectively plant material and polyethers or polyester is the mmole number of the pairing OH base of water of unit mass, is 55.6 (mmOl/g); WNCO is the formula weight of NCO group, is 42 (g/mol); PNCO is the shared percentage composition of NCO group in the MDI product, is 30.7%
The preparation of 1-4 polyurethane foam
Add a certain amount of plant liquefaction thing in 50 gram polyethers propylene oxide or polyester, the even back of high-speed stirring is placed down at 25 ℃ and was made it fully expanded in 1-2 hour.Add amine and organo-metallic tin class catalyzer, silicone oil and as the water of whipping agent, under high-speed stirring, it is mixed, and an amount of MDI of adding reacts under high-speed stirring, continue to be stirred to when having bubble to produce slightly in the mould of going into preheating, put into baking oven, it was solidified 10 minutes.Solidify and measure its performance a week is placed in the back in room temperature (25 ℃) after, between 6.8-8.5mmcl/gj, satisfy the synthetic requirement of medium tenacity urethane hydroxyl.
The control and the optimization of 1-5 mao bamboon powder liquefaction condition
Mao bamboon is one of raw material of the most difficult liquefaction in many natural plant raw materials, and its hemicellulose level is higher.Owing to must add the mao bamboon powder in the crushing process of China fir powder for pulverizing auxiliary material, therefore, on the basis to Mierocrystalline cellulose liquefaction research, we have selected mao bamboon to be the breach as natural discarded plant raw material liquefaction research.Under the effect of catalyzer, mao bamboon can well be liquefied in PEG400, and the hydroxyl value of liquefaction thing is about about 4.5mmol/g.Can satisfy rigid polyurethane foam synthetic needs.But the urethane of pure wool bamboo liquefaction thing because its color is black but also some is crisp, therefore selects suitable market segment to be still waiting further exploration.
Experimental result shows: the liquefaction of plant material is pressed the China fir powder, is mixed wood powder, China fir/mao bamboon compound, the mao bamboon powder be preface from easy to difficult, this is because due to its The Nomenclature Composition and Structure of Complexes difference.(seeing Table 1)
Increase along with mao bamboon powder content in the plant material.The minimizing of content of cellulose causes the decline of liquefaction reaction homogeneity and makes liquefaction difficulty further.Therefore can not surpass two one-tenth in the ratio of the complex liquid chemical industry mao bamboon powder of China fir/mao bamboon be to pay particular attention to.
Two, the technology controlling and process of weedtree plant polyatomic alcohol preparation
The influence of 2-1 catalyzer, temperature and liquor ratio
China fir liquefaction slag content reduces with the increase of catalyst levels, the rising of liquefaction temperature and the increase of liquor ratio.Mao bamboon fiber under similarity condition has shown similar result, and their liquefaction is all approximate carries out its reaction rate constant and minimum slag content (seeing Table 2) by first order reaction kinetic
Table 2 liquefaction condition is to the influence of reactivity constant and minimum slag content
By the rate constant size as can be seen, under identical condition, the China fir fiber liquefies easily than mao bamboon fiber, and this is because their The Nomenclature Composition and Structure of Complexes difference causes. and the mao bamboon main component is a bast-fibre, belong to the phloem fiber raw material, not only fiber is extremely long, and mean length is 18mm～120mm, and cellulosic degree of polymerization is very high, has very outstanding tenacity, therefore the raw material of Chang Zuowei height paper product still will use when the preparation plant polyatomic alcohol, also has many research and developments to do.
The variation research of 2-2 hydroxyl value and acid number
Japan scholar T.Yamada report, in the presence of ethylene glycol (EG) in the Mierocrystalline cellulose liquefaction process generation alcoholysis reaction, also be accompanied by the carrying out of oxidation, and the decline of the thing hydroxyl value that causes liquefying. and though acid number has the trend China fir of rising and the hydroxyl value of mao bamboon to remain unchanged substantially in our liquefaction system, the liquefaction that body series is described also is based on alcoholysis reaction, the liquefied reagent structure has been introduced PEG400 can reduce cellulosic molecular weight to the long chain cellulose alcoholysis process, introduced the PEG segment in the cellulosic structure simultaneously, its solubleness in liquefied reagent is increased, thereby reach the purpose of liquefaction, improve liquor ratio, the same constant result of hydroxyl value that shows. these explanation liquefaction systems are based on alcoholysis reaction, oxidizing reaction is inferior, and Kyoto Univ Japan has reported the very big result of wood powder liquefaction process hydroxyl value decline, so this liquefaction condition can have been created condition for the plant polyatomic alcohol that meets the synthetic requirement of urethane is provided.
The increase of acid number is that hydroxyl value also has slight reducing owing to due to the oxidation of hydroxyl value, still in the liquefaction later stage trend that slows down is arranged, and this may be the reason that has the reaction of esterification, in order to further specify this point, liquefied product is carried out infrared analysis.
The sign of 2-3 polyether glycol
From the FTIR of China fir weedtree raw material and its 60min liquefaction thing residue as can be seen: compare with raw material, liquefied residue has shown strong absorption peak in the hydroxyl at 1720cm-1 place, and illustrate liquefies the generation of hydroxyl afterwards, and partly cause may be due to the hydroxyl oxidize.Therefore fiber is easy to take place oxidizing reaction, there is alcoholic extract hydroxyl group on its each D-glucosyl group C2, C3 and the C6, when oxygenant acts on fiber, generate aldehyde radical, ketone group or hydroxyl according to the different condition phase reaction, and under the strong oxidation of the vitriol oil, increase acid number thereby hydroxyl is easy to be oxidized to hydroxyl.Therefore should strict control sulfuric acid amount in liquefaction.
Find stronger by FTIR in the stretching vibration of 1720cm-1 place hydroxyl, absorption peak strengthens gradually with liquefaction, and in 1220cm-1 and 1720cm-1 place ester bond absorption peak among the C-O, carrying out with liquefaction, obviously strengthen, illustrate that the 1720cm-hydroxyl peak strengthens the generation that also can ascribe ester bond to, this result and the rising in acid number later stage slow down and the result who slightly reduces of hydroxyl value matches.Therefore, cellulosic liquefaction thing is a polyester ether polylol in this research.
The preparation of 2-4 cellulosic polyurethane
Carry out the foaming of plant urethane according to the basic recipe of following table, the urethane compressive strength depends on density to a great extent usually, in order more reasonably to weigh the performance of urethane foam, adopts the relative compressive strength of ratio value representation with compressive strength/density.Along with plant material content increases, its performance also improves.At amount of water hour, the superior performance sex expression is particularly evident.This is because the singularity of plant material composition causes, the cellulosic degree of polymerization height, and fiber is longer, and macrofiber has played good reinforcing effect in urethane foam; And macrofiber is the fine paper making raw material, in the paper making pulp pulping process, in order to improve pulping yield, makes the pulp beating performance to paper properties good side chain be arranged.Pendant hydroxyl group and MDI reaction forms cross-linked structure preferably during foaming, and the mechanical property of foams is strengthened.Therefore, plant material content height, this reinforcing effect is obvious more.
Three, test results and analysis
The character of 3-1 liquefaction polyvalent alcohol
Weedtree, the hydroxyl value of mao bamboon liquefaction polyvalent alcohol is 6.8-8.2mmol/g, satisfies the synthetic requirement to hydroxyl of medium tenacity urethane.Usually in liquefaction reactions such as starch, Mierocrystalline cellulose and sugarcane, tend to follow condensation reactions such as esterification, and the hydroxyl value of liquefaction polyvalent alcohol is reduced and viscosity, also can reduce liquefaction efficiency when serious.And under the liquefaction condition of this experiment, all do not observe 1730cm in the infrared spectrum of assorted China fir/mao bamboon liquefaction polyvalent alcohol
-1The ester carbonyl group peak at place illustrate the esterification of having avoided losing hydroxyl in body series, and this may be due to the introducing of mao bamboon structure.With this synthetic urethane should be polyether(poly)urethane.
The 3-2 mechanical property is analyzed
Along with mao bamboon mass percent (WTA%) in the plant material increases, the tensile strength (σ of China fir urethane
b) and Young's modulus (E) all progressively rise thereupon, and be that 40% place demonstrates maximum value at mao bamboon content. and extension at break
Being whole downtrending. the mao bamboon composition might play a part linking agent in China fir urethane, when the increase of mao bamboon content, the urethane crosslinks dot density increases, and causes σ
bRise with E, this is because mao bamboon is the natural molecule that is rich in benzene ring structure, and is comparatively favourable to the raising of material stiffness, but too much add the ratio that the affiliation adding can destroy the soft or hard section and make degradation. therefore, obtain in the development research of this project, the ratio of mao bamboon powder should be advisable 20%.
The tensile strength of Bao Dao starch polyurethane film was lower in the past, was about 4Mpa, and we as auxiliary liquefied reagent and linking agent, to improve its cross-linking density, make the σ of material with glycerol in the preliminary experiment of this research
bBring up to 16.0Mpa and 48.3Mpa respectively with E.By the effect of mao bamboon performance, σ
bCan be further enhanced with E.The raising of the mechanical property of materials is subjected to the influence of composite factors such as the interaction of molecules between cross-linking set quantity, soft or hard section ratio, the different components, the factor that is separated and strongization of hydrogen degree to a great extent.When mao bamboon content reached 20%, above various effects may be brought into play largely.But the affiliation that adds of mao bamboon causes darkening and embrittlement of urethane, therefore should be specifically noted that in the compound liquefaction of China fir/mao bamboon.
3-3 urethane crosslinks network cross-linked degree (gel content) and cross-linked network two dimension swelling capacity
The China fir composition has a significant impact the performance of urethane, and the crosslinking degree in the cross-linked network structure is the principal element that influences material property.Select the good acetone of liquefaction thing solubility property is measured degree of crosslinking and two-dimentional swelling capacity as solvent at this, in the acetone solvent volatilization process, isocyanic ester occurs in crosslinking reaction with the liquefaction polyvalent alcohol and generates crosslinked urethane, makes the film can only swelling in acetone and can not dissolve just because of the existence of urethane crosslinks structure.
Along with the mass ratio increase of China fir, gel content obviously rises.The result of study of Mierocrystalline cellulose model compound and benzene isocyanate reaction mechanism shows: Mierocrystalline cellulose with the reaction of isocyanic ester in, can be effective as the crosslinking reaction that a kind of linking agent participates in urethane, therefore the increase of China fir content, being the increase of cross-linking set number, is the immediate cause that causes gel content to rise.
The swelling capacity of PU in solvent also is the another kind of effective means of the crosslinking degree of characterization of membrane in addition, and along with the increase of China fir mass ratio in the liquefaction thing, the two-dimentional solubility of film in acetone reduces gradually.This is consistent with the result that the gel content of polyurethane film increases.
The strong effect of the intermolecular hydrogen of 3-4
Along with the increase of China fir content, near the displacement that absorbs honeybee the 3300cm-1 presented by high wave number to lower wave number return high wave number variation tendency (that is: 3354,3318,3308,3298,3308,3380cm-1).This shows that the strong effect of molecular hydrogen is arranged between the China fir component.The importing of China fir composition has improved the strong effect of hydrogen between polyurethane molecular, and it is maximum to be at content that its effect in 40% o'clock reaches, and too much adding can reduce the strong effect of intermolecular hydrogen on the contrary again.This Changing Pattern is consistent with the result of variations of mechanical property.
In addition, the ammonia ester is strong to be that the basic function of urethane is strong, and occurs near 1730cm-1, can be split into free ammonia ester strong (1730cm-1) and strongization of hydrogen ammonia ester is good for (1707cm-1) because the strong effect ammonia ester of hydrogen is strong.The absorption peak of the strong coupling carbonyl of hydrogen was at the 1707cm-1 place during the ammonia ester was strong, and this hydrogen strong be in hard section mutually in, the specific absorbance of these two kinds of carbonyl absorption peaks is about the same, thereby can weigh strongization of hydrogen degree with following experimental formula according to the area at these two peaks:
Increase along with China fir content, strongization of hydrogen degree constantly strengthens (table 3), the ratio of hard section improves with the increase of China fir composition in the also explanation system of this result, thus the intermolecular interaction that has improved material, and this raising to the mechanical property of materials is also very favourable.
Strongization of the hydrogen degree of table 3 China fir urethane
| Content (%) | 0 | 20 | 40 | 60 | 80 | 100 |
| (Xb)co | 0.047 | 0.132 | 0.168 | 0.249 | 0.280 | 0.347 |
The 3-5 thermostability
China fir urethane uses as material, and except mechanical property, thermostability also is one of important condition, and weight analysis is the common method that thermostability characterizes.The China fir composition is incorporated into the resistance toheat that can improve material in the urethane greatly, and this result of study shows that it is very big that the importing of China fir can make the complete decomposition temperature of plant urethane have.In addition, the thermostability of material also can speed temperature (Tmax) and integrator decomposition temperature (IPDT) be estimated all the time by maximum.Along with the increase of China fir component content, IPDT significantly improves.Its decomposition course is broadly divided into four steps.The first step decomposition occurs in 80-223 ℃, this part mass loss mainly is due to the desorb of solvent in the polymkeric substance, second step and the 3rd step mainly are that the pyrolysis of polymkeric substance and the depolymerization of cross-linked network cause, and the 4th step weight loss occurs in after 400 ℃, shows the decomposition of polymer network.
3-6 scanning electron microscope analysis (SEM)
Usually thermostability and each compatibility between components of sample of material have confidential relation, so observe its thermostability of reflection that the consistency of each sample can be indirect by scanning electron microscope.
The scanning electron microscope sheet of each sample surface of fracture is summarized in Fig. 1. and China fir urethane (A) has presented two phase structure clearly, and network structure is irregularity also.Along with the importing interface of mao bamboon composition become fuzzy, (B) interface completely dissolve when mao bamboon content reaches 20%, compact structure, illustrate this moment China fir urethane mutually and mao bamboon urethane is mutual fully mutually melts.But adding, too much mao bamboon will progressively get back to original state (C) again.The result shows when mao bamboon and the mixed liquefied back of China fir synthesis of polyurethane, but China fir urethane network and mao bamboon urethane network interpenetration are filled up the hole, this is very favourable to the mechanical property that improves material.
The 3-7 degradation property
Weedtree urethane is a kind of typical biodegradable material, but as material in use, the control of biodegradation rate and the water resisting property of assurance and material is seemed particularly important.It is a kind of method of solution that the compound that adds non-degraded therein comes control degradation speed, but non-degradation compound may reproduce into secondary pollution.This result of study shows: degradable natural China fir can be regulated the degradation speed of urethane.
Near in the sample infrared spectra after 7 week of degraded the 3300cm-1 absorption peak all moves (with comparing before the degraded) to high wave number, and hydrogen bond all weakens between the sample molecule of explanation degraded back thus.The more basic disappearance of urethane urethane (1730cm-1) after degraded of China fir in addition, and the high urethane of mao bamboon content has kept more relatively ammonia ester bond.The result shows that the China fir ammonia ester bond degrades easily, therefore be expected to obtain to satisfy the degradable polyurethane material of different service requirementss by the adjustment of its synthetic ratio.
The research of weedtree urethane microbiological deterioration mechanism
Polyurethane foamed material adopts following method to carry out in the degradation in soil experiment:
Polyurethane foam is cut into the square sample several piece of 20mm, in placing into the soil after the weighing, every the sampling in January, the earth of brush district, dry back surface attachment, weighing once more, the rate of loss of calculated weight.
Because the complicacy of plant material composition and the diversity of microorganism, the very complicated present unified test and evaluation standard that also do not have of mechanism of degradation. in order to study the degradation rule of plant urethane, we investigate from Hong Guan microcosmic surface and three aspects of immanent structure.
On the macroscopic view, we weigh by mass loss the most intuitively and compressive strength loss, in the time of along with polyurethane structural, mass loss obviously increases, at the degraded initial stage, it is very fast that the quality of urethane foam reduces speed, and the speed of decreased later is slack-off a bit. and this may be the degraded later stage, the deep layer of microorganism enters with the degradation production deep layer and discharges gradually due to the difficulty. and the variation tendency and the mass loss of loss of compression are similar, but the loss of compressive strength will be much larger than corresponding mass loss
Can observe by SEM in the soil microbial degradation process of China fir urethane, the microcosmic surface morphology change as shown in the figure, Fig. 1 is a complete uniform microvoid structure before the soil microbial degradation, carrying out along with degraded, not only urethane intensity obviously descends, and microvoid structure progressively destroyed, and hole wall also suffers breakage, and polyurethane structural network space progressively becomes sees Fig. 2 Fig. 3 greatly.More what is interesting is and destroying comparatively serious hole place, can find that after amplifying many mycelia or bacterium colony see Fig. 4.Destroyed more serious sample and fluff and become fragile, can't be measured its intensity, therefore only this sample quality loss is investigated.
In order further to characterize the variation of plant urethane its immanent structure in degradation process, the hydrogen bond that we have investigated in the microbiological deterioration process changes.This is that it is concerning the accumulation shape of polyurethane high molecule chain, to microbic resolvability also important influence because hydrogen bond has important effect in polyurethane structural.
The existence of hydrogen bond, making the infrared absorption peak of C=O compare with general C=O absorption peak can divide, and becomes bimodally, and this peak also can move to the lower wave number direction simultaneously.IR collection of illustrative plates by urethane, as can be seen after urethane is handled through soil microorganisms, the splitting degree of this absorption peak obviously weakens, be moved to high wave number direction simultaneously, hydrogen bond in this explanation ammonia ester bond obviously weakens, and in TMP-PU not this phenomenon occur, this means that being accompanied by hydrogen bond in the microbiological deterioration process weakens, and weakening of hydrogen bond made things convenient for microorganism that the deep layer of PU is entered.
From the IR spectrogram, can carry out semi-quantitative analysis to the Strength Changes of hydrogen bond.Under the effect of hydrogen bond, the C=O base on the hard section ammonia ester is split into two stretching vibration peaks, wherein is free C=O base stretching vibration absorption peak about 1730cm-1, is the C=O base stretching vibration absorption peak of hydrogen bonding about 1730cm-1.In addition.Be the C=O stretching vibration absorption peak of hydrogen bonding on the hard section urea groups about 1660cm-1, and the C=O absorption peak of free urea groups can't be observed from the FTIR collection of illustrative plates.
The absorption peak of hydrogen bond coupling carbonyl is at the 1703cm-1 place in the ammonia ester bond, show this hydrogen bond be in hard section mutually in the absorption peak of free carbonyl at the 1730cm-1 place, the specific absorbance of these two kinds of carbonyl absorption peaks is about the same, thereby can weigh hydrogen bonding degree [i] with following experimental formula according to the area at these two peaks:
Hard section force of cohesion index:
In the formula: (Af) CO, (Ab) CO is respectively the absorption peak area of the C=O of free and hydrogen bonding; Aua is the absorption peak area of urea C=O; A1600 is the absorption peak area of phenyl ring C=C.
This calculation result is summarized among the Table3, and along with the prolongation of degradation time, (Xb) CO and the Ch of WT-PU are obviously reducing, and illustrates that the hydrogen bond between the hard section in degraded back weakens to some extent.These two indexs have characterized pure hard intersegmental hydrogen bonding degree from different sides, they all do not consider the ethers hydrogen bond.Pertinent data shows that after hard segment content reached certain numerical value, most of hydrogen bond was present in hard intersegmental part, but and therefore produces being separated between the urethane soft or hard.Therefore import this composition of China fir in PU, can reduce hard section hydrogen bonding degree under the effect of soil microorganisms, along with weakening of hydrogen bond, the degree that is separated of this soft or hard section also weakens to some extent, thereby more helps the Degradation of microorganism to its PU.
Four, pilot process condition
1) get the raw materials ready: plant material must melt the back and use greater than 80 orders when industrial chemicals solidified as winter.
2) reinforced: plant material divides three times and evenly adds, and does 600 kilograms in every still, adds principal reaction inventory error less than 2 kilograms, and the catalyzer error is less than 0.2 kilogram
3) heat up: about 140 ℃ (but will decide as the case may be sometimes) of reactor intensification
4) insulation: about 60 minutes.
According to above result of study following three prescriptions are proposed
| 1. plant polyatomic alcohol prescription | (I)2512 | (II)1689 | Remarks |
| Weedtree/mao bamboon (8/2) | Mix wood powder | ||
| Poly(oxyethylene glycol) 400 | 200 | 200 | Technical grade |
| Glycol ether | 20 | 22 | Technical grade |
| Glycerine (medical grade) | 100 | 60 | Medical grade |
| Plant activator | 5.4 | 5.6 | Our company provides |
| Biodegradable polyester | 35-55 | 30-45 | Can adjust on request |
| The plant powder | 82-110 | 90-140 | According to the viscosity adjustment |
| 2. plant polyatomic alcohol index | |||
| Hydroxyl is planted (mgKOH/g) | 550-600 | 450-490 | |
| Viscosity | 3600-4200 | 2600-4500 | |
| Colourity | Dark brown | Dark brown |
Foam performance index (, adjusting foaming formulation) by user's service requirements
Density (kg/m
3) 30-150
Thermal conductivity (mW/ (m.k)) is less than 0.024
Compressive strength: Kpa 150-250
Oxygen index: 24-32.
Claims (1)
1, plant polyatomic alcohol polyurethane rigid foam, it is characterized in that making step is: (1) puts into the drying machine drying with weedtree, mao bamboon; (2) putting into pulverizer by weedtree and mao bamboon weight ratio 4: 1～0.8 proportioning pulverizes; (3) the crushed mixed powder material is filtered out powder mix below the 80 purpose fineness through sieve shaker; (4) by weight with powder mix 700～800kg, polyoxyethylene glycol 350～400kg, glycol ether 18.7～19kg, glycerine (medical grade) 70～80kg, plant activator 5.5～6kg, biological degradation ester 20～40kg, plant powder 80～120kg feeds intake and liquefies to reactor, produces plant polyatomic alcohol; (5) by weight plant polyatomic alcohol 35～40kg, polyethers 20～25kg, polyester 15～20kg, whipping agent 141b18kg, varies catalyzer 2.3kg, silicone oil 1.5～2kg, linking agent 6～7kg, water 0.5kg, PZA (six hydrogen, three dais) 0.5～1kg, tensio-active agent 2～3kg uniform mixing are formed the foaming base-material; (6) will foam base-material and isocyanic ester PAPI by weight 1: 1.2～1.3 and catalyzer, water inject respectively that cavity hybrid reaction forms hard polyurethane foam in spray gun or the injection moulding machine.
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| CN103788327B (en) * | 2014-01-29 | 2016-03-02 | 中国林业科学研究院亚热带林业研究所 | Bamboo leftover microwave liquefied product prepares the method for hard polyurethane foam |
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