CN102241826A - Modified lignin and urea-formaldehyde resin synthesized from same and preparation methods of modified lignin and urea-formaldehyde resin - Google Patents
Modified lignin and urea-formaldehyde resin synthesized from same and preparation methods of modified lignin and urea-formaldehyde resin Download PDFInfo
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Abstract
The invention discloses a modified lignin and a urea-formaldehyde resin synthesized from same and preparation methods of the modified lignin and the urea-formaldehyde resin, belonging to the field of bonding agents used in wood processing. A technological synthetic route with weak base-weak acid-weak base is adopted, the molar ratio of formaldehyde to urea is controlled during an addition stage to generate a reasonable structure, the modified lignin as well as residual hydroxymethyl and free formaldehyde are added at the later stage of reaction in order to accomplish reaction, thus the content of methylene ether link (-CH2-O-CH2-) and the content of hydroxymethyl in the resin are reduced to a certain extent, the formaldehyde emission of the resin is lowered, and simultaneously, higher bonding strength and water resistance are ensured. The urea-formaldehyde resin in the invention is simple and brief in process and low in cost, the formaldehyde emission of the plate prepared by adopting the bonding agent reaches the E0-level standard and the plate can maintain high bonding strength after being cooked in hot water. The modified lignin is simple in synthesis method and low in cost and is especially suitable for the modification of the urea-formaldehyde resin with low molar ratio.
Description
Technical field
The present invention relates to a kind of modified lignin resin, synthesize urea-formaldehyde resin adhesive and the preparation method of the two with modified lignin resin, this sizing agent is applicable to the sizing agent of the required usefulness of wood working.
Background technology
China's wood-based plate ultimate production has surpassed 11,300 ten thousand m at present
3, to surpass 10% speed increment, having become the big wood-based plate of the first in the world producing country every year on average, Wood-based Panel Production sticks with glue agent annual consumption (100% solid content meter) and has surpassed 8,000,000 t.Urea-formaldehyde resin adhesive is owing to its raw material is easy to get, with low costly becomes the tamanori that wood industry is most widely used, consumption is maximum.But, because residual a large amount of free formaldehydes in the urea-formaldehyde resin, exist methylene ether and methylol etc. can decomposite the unstable group of formaldehyde on its polymer chain structure simultaneously, the wood-based plate that causes urea-formaldehyde resin preparation is environment release formaldehyde constantly towards periphery in use, and long-term serious harm people's is healthy.Therefore, China has issued mandatory standard GB 18580-2001 December calendar year 2001, and regulation wood-based plate and goods burst size of methanal thereof must reach the E1 level and the E2 level just can be used for indoor.And increased E in 2004
0The standard of level (the sheet material burst size of methanal of moisture eliminator method measurement≤0.5mg/L), integrate with international standard.
Xylogen is easy to get and is widely used in the modification of urea-formaldehyde resin because of cheap, raw material.Its purpose mainly is to improve the water-fast intensity of urea-formaldehyde resin, can reduce the cost of urea-formaldehyde resin simultaneously again; The investigator who also has makes xylogen become a kind of effective formaldehyde adsorbent by the modification to xylogen, has played the effect that reduces formaldehyde.Hydroxymethylation takes place with calcium lignin sulphonate and formaldehyde and generates methylolated xylogen and made a kind of nontoxic sizing agent with urea, trimeric cyanamide, remaining formaldehyde reaction again in US50755402 under strong acid condition, this sizing agent can be applied in the feed of animal.US6291558 utilizes xylogen and formaldehyde and a kind of undersaturated carbonyl compound reaction to make a kind of sizing agent, and this sizing agent can directly apply to plank processing and also can join in the urea-formaldehyde resin.US3994850 at first mixes xylogen with commercially available urea-formaldehyde resin, under certain condition, add urea by substep and reduce formaldehyde in the urea-formaldehyde resin, finally makes the sizing agent that low formaldehyde discharges.US4244846 makes the timber sizing agent that low formaldehyde discharges with the xylogen copolymerization after urea-formaldehyde resin and the modification.US2622979 reacts urea and formaldehyde to for some time under weak basic condition, add a certain amount of sulfonated lignin then, stirring for some time is adjusted to slightly acidic with system and reacts to Gardner viscosity Q, adds ethanol at last, has made the sizing agent that strengthens the paper wet tenacity.US4332589 utilizes the hydroxymethylation that carries out xylogen under the present alkaline condition of the hydroxymethylation of xylogen and formaldehyde to make methylolated xylogen generation copolymerization then under strong acid condition, has made this dispersion agent of a kind of dispersion agent and can be applied to dyeing.
These traditional method of modifying can increase the manufacturing cost of sizing agent on the one hand, can not satisfy environmental protection and high-intensity requirement simultaneously on the one hand.Still a large amount of free formaldehydes, unsettled methylene ether link and methylol groups have been kept in the sizing agent that much makes, reversible reaction can take place in the use of resin, environment release formaldehyde towards periphery, and this process is very long persistent, can serious harm healthy to people.Or but burst size of methanal is very low can not reach the ideal bonding strength.So, on the basis that guarantees high bonding strength, reduce the urea-formaldehyde resin burst size of methanal and become current Study on urea-formaldehyde focus.
Synthetic modified lignin resin of the present invention can guarantee that urea-formaldehyde resin has very high bonding strength, and can reduce the burst size of methanal of resin on this basis significantly, reaches the standard of E0 level, has very low cost simultaneously.
Summary of the invention
The present invention at first utilizes lignin derivative to synthesize a kind of modified lignin resin, adopt traditional weak base-weak acid-weakly alkaline synthesis route, add modified lignin resin in the reaction later stage and guarantee that resin has good consolidation strength and than low burst size of methanal, the tackiness agent burst size of methanal that makes reaches E
0Grade standard.
A kind of modified lignin resin is characterized in that: be that 40%-60% lignin derivative aqueous solution 120-160 part, aldehyde 20-60 part, lignin modification agent 5-30 part, xylogen activator 0.2-1.5 part are formed by mass percent concentration by weight;
Lignin derivative is one or more mixing by any ratio in sodium lignosulfonate, calcium lignin sulphonate, ammonium lignosulphonate, magnesium lignosulfonate, the alkali lignin;
Aldehyde be mass percent concentration be 35%-37% formaldehyde, 38%-40% acetaldehyde, 38%-40% oxalic dialdehyde, one or more mixing in the 50%-52% glutaraldehyde, 40%-42% propenal, 38%-40% furfural by any ratio;
The lignin modification agent is acrylamide, quadrol, trolamine, trimeric cyanamide, 1, and one or more in 4-butanediamine, thiocarbamide, the urea are by the mixing of any ratio.
The xylogen activator is one of 20%-25% aqueous sodium hydroxide solution, the 20%-25% trolamine aqueous solution, 20%-25% vulkacit H aqueous solution.
The preparation method of described modified lignin resin is characterized in that step is as follows:
Step 1: the massfraction of preparation 120-160 weight part is the lignin derivative aqueous solution of 40%-60%, adds 0.1-1 weight part xylogen activator, places the product that obtained step 1 in 1-48 hour.
Step 2: in the product of step 1, add the aldehyde of 20-60 weight part, at 50 ℃-85 ℃ reaction 30-120min, during keep the pH value of system to obtain the product of step 2 for 8.5-11;
Step 3: add the lignin modification agent of 5-30 weight part in the product of step 2, the xylogen activator that adds the 0.1-0.5 weight part reacted 1-5 hour under 50 ℃-85 ℃.Cooling, discharging.
Use the urea-formaldehyde resin of described modified lignin resin, it is characterized in that: form by modified lignin resin 10-60 part, mass percent concentration 35%-37% formalin 160-208 part, 120 parts in urea, basic catalyst 0.02-0.05 part, an acidic catalyst 0.02-0.05 part, formaldehyde adsorbent 0.05-5 part by weight.
Basic catalyst is one of 20%-25% aqueous sodium hydroxide solution, the 20%-25% trolamine aqueous solution, the 20%-25% vulkacit H aqueous solution of mass percent concentration.
An acidic catalyst is one of 30%-35% aqueous formic acid, 30%-35% acetic acid aqueous solution, 5%-10% aqueous sulfuric acid, 20%-25% aqueous hydrochloric acid of mass percent concentration.
Formaldehyde adsorbent is one or more mixing by any ratio in trimeric cyanamide, acrylamide, polyvinyl alcohol, thiocarbamide, phenol, xylogen powder, tree bark powder, tannin, the starch.
The preparation method of described urea-formaldehyde resin is characterized in that step is as follows:
(1): the mass percent concentration 35%-37% formalin that in container, adds the 160-208 weight part, urea 60 weight parts, the formaldehyde in control addition stage and the mol ratio of urea are at 1.6-2.0, start whipping appts, regulate pH=9.0-9.3 with basic catalyst, be warming up to 85 ℃-95 ℃, insulation reaction half an hour;
(2): regulate pH=4.8-5.2 with an acidic catalyst, reaction 10min;
(3): add the urea of 20-40 weight part again, reaction 5min-20min. reacts to terminal, and adding basic catalyst adjusting pH value is 6.5-7.5;
(4): add the modified lignin resin of 10-60 weight part, under 85 ℃ of-95 ℃ of conditions, react 10-60min;
(5): be cooled to 60-80 ℃, add remaining 20-40 weight part urea and 0.05-5 parts by weight of formaldehyde sorbent material, reaction 10-40min;
(6): be cooled to below 40 ℃, regulate the pH value between 7.0-7.5, cooling discharging.
Environment-friendly urea-formaldehyde resin of the present invention is in the impregnation application process, described tackiness agent is by 100 weight part urea-formaldehyde resins, 15 weight part fillers (as starch, flour etc.), 5 weight part solidifying agent are made, and wherein solidifying agent is that mass percent concentration is 20% ammonia chloride or ammonium persulfate solution or ammonium acetate-ammonium persulphate composite curing agent.
Advantages such as the urea-formaldehyde resin of the present invention's preparation has free formaldehyde content low, and storage period is moderate, and technology is succinct, and the reaction times is short, and is with low cost, the sheet material burst size of methanal of this tackiness agent preparation reaches E
0Grade standard, and behind the hot cooking, still keep high consolidation strength.
Be lower than the about 737-1037 of environment protection type urea formaldehyde resin price unit on the market on the urea-formaldehyde resin adhesive price of this preparation method preparation.Under the prerequisite that guarantees environmental protection, reduce cost again, had good market outlook.
Description of drawings
The infrared comparison diagram A of Fig. 1 xylogen and modified lignin resin (wave number 1800cm
-1-200cm
-1)
The infrared comparison diagram B of Fig. 2 xylogen and modified lignin resin (wave number 4000cm
-1-1800cm
-1)
Fig. 3 UF's
13The C nuclear magnetic spectrogram
Fig. 4 L-UF
13The C nuclear magnetic spectrogram
(the common urea-formaldehyde resin of UF-wherein; L-UF-modified lignin resin modified urea-formaldehyde resin).
Embodiment
Embodiment 1
Add the 70g sodium lignosulfonate in the beaker, add 85.5g water, be mixed with the aqueous solution, adding 0.2g massfraction is 20% aqueous sodium hydroxide solution, after shaking up, leaves standstill 12 hours.
With the 141g massfraction is that 45% lignin liquor joins in the 500ml four-hole boiling flask, opens whipping appts, is warming up to 70 ℃, adds the 30g massfraction and be 37.45% formalin, keeps the pH=9.5 of system, after temperature rises to 70 ℃, and insulation 60min; Add the 19.5g trimeric cyanamide, the pH=9.5 of regulation system reacted cooling discharging 3 hours.
In the 500ml four-hole bottle of reflux condensate device and whipping appts is housed, add 37.45% formalin 168.39g, urea 63.03g opens whipping appts, drips 20% aqueous sodium hydroxide solution regulation system pH=9.2, begins heating simultaneously; Treat that temperature rises to 85 ℃, insulation reaction half an hour; With 30% aqueous formic acid regulation system pH=4.8, reaction 10min; Add remaining 35.66g urea, reaction 15min; PH value=7.2 of aqueous sodium hydroxide solution regulation system with 20%; Add above-mentioned modified lignin resin 18.50g, reaction 40min; Be cooled to 75 ℃, add 21.44g urea and 3g trimeric cyanamide, reaction 20min; Be cooled to 40 ℃, regulation system pH value is 7.2, and cooling discharging obtains urea-formaldehyde resin adhesive.Total mol ratio of this system formaldehyde and urea is 1.05: 1, and addition stage at initial stage control F/U mol ratio is 2.0: 1.This urea-formaldehyde resin is in application, and described tackiness agent is made by 20% (mass percentage concentration) ammonium chloride of the urea-formaldehyde resin of 100 weight parts, the filler of 15 weight parts (flour or starch), 5 weight parts.
Embodiment 2
During the present embodiment modified lignin resin was synthetic, the massfraction of lignosulfonic acid sodium water solution was 40%, and add-on is 120 weight parts, and other are identical with embodiment 1.
Embodiment 3
During the present embodiment modified lignin resin was synthetic, the massfraction of lignosulfonic acid sodium water solution was 40%, and add-on is 160 weight parts, and other are identical with embodiment 1.
Embodiment 4
During the present embodiment modified lignin resin was synthetic, the massfraction of lignosulfonic acid sodium water solution was 60%, and add-on is 120 weight parts, and other are identical with embodiment 1.
Embodiment 5
During the present embodiment modified lignin resin was synthetic, the massfraction of lignosulfonic acid sodium water solution was 60%, and add-on is 160 weight parts, and other are identical with embodiment 1.
Embodiment 6
During the present embodiment modified lignin resin was synthetic, the add-on of xylogen activator was 0.1 weight part, and other are identical with embodiment 1.
Embodiment 7
During the present embodiment modified lignin resin was synthetic, the add-on of xylogen activator was 1 weight part, and other are identical with embodiment 1.
During the present embodiment modified lignin resin was synthetic, the lignosulfonic acid sodium water solution left standstill under alkaline environment 1 hour, and other are identical with embodiment 1.
Embodiment 9
During the present embodiment modified lignin resin was synthetic, the lignosulfonic acid sodium water solution left standstill under alkaline environment 48 hours, and other are identical with embodiment 1.
Embodiment 10
During the present embodiment modified lignin resin was synthetic, the add-on of aldehyde was 20 weight parts, and other are identical with embodiment 1.
Embodiment 11
During the present embodiment modified lignin resin was synthetic, the add-on of aldehyde was 60 weight parts, and other are identical with embodiment 1.
Embodiment 12
The synthesis temperature of present embodiment modified lignin resin is 50 ℃, and other are identical with embodiment 1.
Embodiment 13
The synthesis temperature of present embodiment modified lignin resin is 85 ℃, and other are identical with embodiment 1.
Embodiment 14
During the present embodiment modified lignin resin was synthetic, the reaction times of lignosulfonic acid sodium water solution and aldehyde was 30 minutes, and other are identical with embodiment 1.
Embodiment 15
During the present embodiment modified lignin resin was synthetic, the reaction times of lignosulfonic acid sodium water solution and aldehyde was 120 minutes, and other are identical with embodiment 1.
Embodiment 16
During the present embodiment modified lignin resin was synthetic, system pH was 8.5, and other are identical with embodiment 1.
Embodiment 17
During the present embodiment modified lignin resin was synthetic, system pH was 11, and other are identical with embodiment 1.
Embodiment 18
During the present embodiment modified lignin resin was synthetic, the properties-correcting agent add-on was 5 weight parts, and other are identical with embodiment 1.
Embodiment 19
During the present embodiment modified lignin resin was synthetic, the properties-correcting agent add-on was 30 weight parts, and other are identical with embodiment 1.
Embodiment 20
During the present embodiment modified lignin resin was synthetic, after the lignin modification agent added, the add-on of xylogen activator was 0.1 weight part, and other are identical with embodiment 1.
Embodiment 21
During the present embodiment modified lignin resin was synthetic, after the lignin modification agent added, the add-on of xylogen activator was 0.5 weight part, and other are identical with embodiment 1.
Embodiment 22
During the present embodiment modified lignin resin was synthetic, after the lignin modification agent added, the reaction times was 1 hour, and other are identical with embodiment 1.
Embodiment 23
During the present embodiment modified lignin resin was synthetic, after the lignin modification agent added, the reaction times was 5 hours, and other are identical with embodiment 1.
Embodiment 24
During the present embodiment modified lignin resin is synthetic, adopt calcium lignin sulphonate synthesis modification xylogen, other are identical with embodiment 1.
Embodiment 25
During the present embodiment modified lignin resin is synthetic, adopt lignosulfonic acid ammonia synthesis modified lignin resin, other are identical with embodiment 1.
Embodiment 26
During the present embodiment modified lignin resin is synthetic, adopt magnesium lignosulfonate synthesis modification xylogen, other are identical with embodiment 1.
Embodiment 27
During the present embodiment modified lignin resin is synthetic, adopt alkali lignin synthesis modification xylogen, other are identical with embodiment 1.
Embodiment 28
During the present embodiment modified lignin resin is synthetic, adopt acetaldehyde synthesis modification xylogen, other are identical with embodiment 1.The acidity of acetaldehyde is stronger than formaldehyde, so reactive behavior will be weaker than formaldehyde, and the sheet material bonding strength that records reduces, but has also played the effect that reduces free formaldehyde in the glue simultaneously.
Embodiment 29
During the present embodiment modified lignin resin is synthetic, adopt oxalic dialdehyde synthesis modification xylogen, other are identical with embodiment 1.Because oxalic dialdehyde has strongly-acid, the modified lignin resin reactive behavior is less than the formaldehyde height under alkaline condition, and therefore, the bonding strength of the sheet material that records is relatively low, but avoided residual free formaldehyde in modified lignin resin, made that the free formaldehyde in the final glue reduces.
Embodiment 30
During the present embodiment modified lignin resin is synthetic, adopt glutaraldehyde synthesis modification xylogen, other are identical with embodiment 1.The glutaraldehyde molecular chain is longer than oxalic dialdehyde, and therefore, also not as formaldehyde, the bonding strength of the sheet material that records equally is also relatively low, can avoid the introducing of free formaldehyde in urea-formaldehyde resin equally for reactive behavior, and burst size of methanal reduces.
Embodiment 31
During the present embodiment modified lignin resin is synthetic, adopt propenal synthesis modification xylogen, other are identical with embodiment 1.Bonding strength reduces, and free formaldehyde reduces.
Embodiment 32
During the present embodiment modified lignin resin is synthetic, adopt furfural synthesis modification xylogen, other are identical with embodiment 1.Bonding strength decreases, and free formaldehyde reduces.
Embodiment 33
During the present embodiment modified lignin resin was synthetic, adopting acrylamide was the lignin modification agent, and other are identical with embodiment 1.
Embodiment 34
During the present embodiment modified lignin resin was synthetic, adopting quadrol was the lignin modification agent, and other are identical with embodiment 1.
Embodiment 35
During the present embodiment modified lignin resin was synthetic, adopting trolamine was the lignin modification agent, and other are identical with embodiment 1.
Embodiment 36
During the present embodiment modified lignin resin is synthetic, adopt 1, the 4-butanediamine is the lignin modification agent, and other are identical with embodiment 1.
Embodiment 37
During the present embodiment modified lignin resin is synthetic, adopt 1, the 4-butanediamine is the lignin modification agent, and other are identical with embodiment 1.
Embodiment 38
During the present embodiment modified lignin resin was synthetic, adopting thiocarbamide was the lignin modification agent, and other are identical with embodiment 1.
Embodiment 39
During the present embodiment modified lignin resin was synthetic, adopting urea was the lignin modification agent, and other are identical with embodiment 1.
Embodiment 40
During the present embodiment urea-formaldehyde resin adhesive was synthetic, the modified lignin resin add-on was 10 weight parts, and other are identical with embodiment 1.
Embodiment 41
During the present embodiment urea-formaldehyde resin adhesive was synthetic, the modified lignin resin add-on was 60 weight parts, and other are identical with embodiment 1.
Embodiment 42
During the present embodiment urea-formaldehyde resin adhesive was synthetic, the add-on of formaldehyde adsorbent was 0.05 weight part, and other are identical with embodiment 1.
Embodiment 43
During the present embodiment urea-formaldehyde resin adhesive was synthetic, the add-on of formaldehyde adsorbent was 0.5 weight part, and other are identical with embodiment 1.Active group in the system increases, and shorten the storage period of glue.
Embodiment 44
During the present embodiment urea-formaldehyde resin adhesive is synthetic, be formaldehyde adsorbent with the acrylamide, other are identical with embodiment 1.
Embodiment 45
During the present embodiment urea-formaldehyde resin adhesive is synthetic, be formaldehyde adsorbent with the polyvinyl alcohol, other are identical with embodiment 1.
Embodiment 46
During the present embodiment urea-formaldehyde resin adhesive is synthetic, be formaldehyde adsorbent with the thiocarbamide, other are identical with embodiment 1.
Embodiment 47
During the present embodiment urea-formaldehyde resin adhesive is synthetic, be formaldehyde adsorbent with phenol, other are identical with embodiment 1.
Embodiment 48
During the present embodiment urea-formaldehyde resin adhesive is synthetic, be formaldehyde adsorbent with the xylogen powder, other are identical with embodiment 1.
Embodiment 49
During the present embodiment urea-formaldehyde resin adhesive is synthetic, be formaldehyde adsorbent with the tree bark powder, other are identical with embodiment 1.
During the present embodiment urea-formaldehyde resin adhesive is synthetic, be formaldehyde adsorbent with the tannin, other are identical with embodiment 1.
Embodiment 51
During the present embodiment urea-formaldehyde resin adhesive is synthetic, be formaldehyde adsorbent with starch, other are identical with embodiment 1.
Embodiment 52
During the present embodiment urea-formaldehyde resin adhesive was synthetic, total mol ratio of formaldehyde and urea was 1.0: 1.0, and the initial stage mol ratio is 2.0: 1.0, and other are identical with embodiment 1.
Embodiment 53
During the present embodiment urea-formaldehyde resin adhesive was synthetic, total mol ratio of formaldehyde and urea was 1.3: 1.0, and the initial stage mol ratio is 2.0: 1.0, and other are identical with embodiment 1.Total mole of rising of formaldehyde and urea, shorten the storage period of glue.
Embodiment 54
During the present embodiment urea-formaldehyde resin adhesive was synthetic, total mol ratio of formaldehyde and urea was 1.0: 1.0, and the initial stage mol ratio is 1.6: 1.0, and other are identical with embodiment 1.
Embodiment 55
During the present embodiment urea-formaldehyde resin adhesive was synthetic, total mol ratio of formaldehyde and urea was 1.3: 1.0, and the initial stage mol ratio is 1.6: 1.0, and other are identical with embodiment 1.Total mole of rising of formaldehyde and urea, shorten the storage period of glue.
Embodiment 56
Present embodiment is in adhesive applications, and described tackiness agent is by the urea-formaldehyde resin of 100 weight parts, the filler of 15 weight parts, the composite curing agent of 5 weight parts: 20% ammonium persulphate and 20% ammonium phosphate weight ratio are made at 2: 3, and other are identical with embodiment 1.
Comparative Examples 1
Present embodiment does not add modified lignin resin, and other are identical with embodiment 1.
Comparative Examples 2
Present embodiment does not add formaldehyde adsorbent, and other are identical with embodiment 1.
Attached: the water resistance test of all embodiment, Comparative Examples is to soak by sheet material being put into 63 ℃ of hot water, and whether observing comes unglued is weighed; The numerical value of consolidation strength is sheet material to be put into 63 ℃ of hot water immersions measure after 3 hours.
Table 1 embodiment 1 urea-formaldehyde resin adhesive performance
Table 2 embodiment performance comparison
From Fig. 1 and Fig. 2 as can be seen, among the infrared figure of modified lignin resin, the flexural vibration of imines C=N-H that increased stretching vibration, the 1590.02cm-1 of the imines C=N-H of 3333.89cm-1 are the formation vibration of N-H of aromatic series primary, secondary amine C-N stretching vibration, the 812.06cm-1 of the charateristic avsorption band of trimeric cyanamide triazine ring, 1355.61cm-1.The increase of these peak positions has shown being grafted in the lignin molecule of trimeric cyanamide success.
Fig. 3 urea-formaldehyde resin
13The C nuclear magnetic spectrogram
Comparison diagram 3 and Fig. 4 are as can be known, having increased chemical shift in the urea-formaldehyde resin 13C nuclear magnetic spectrogram after the modified lignin resin modification is six place's absorption peaks of 24.010ppm, 54.543ppm, 68.335ppm, 72.265ppm, 169.981ppm, 179.789ppm, wherein, δ=24.010ppm is the xylan residual alkyl chain of hydrolysis under alkaline condition in the xylogen; δ=169.981ppm is the absorption peak of the alkylbenzene in the xylogen; δ=179.789ppm is the aldehyde radical residual behind the xylan hydrolysis or the absorption peak of ketone; The absorption peak of all the other increases is all the absorption peak of the material of the active group reaction back generation in trimeric cyanamide and the urea-formaldehyde resin.These increases that absorb peak position have illustrated that reaction has taken place for modified lignin resin and urea-formaldehyde resin.
Cost estimating
1, at present the price of (by on March 21st, 2011) urea is about 1850 yuan/ton, the price of industrial formol is about 1600 yuan/ton, the lignin derivative price is about 1800 yuan/ton, the properties-correcting agent price is 11000 yuan/ton, the formaldehyde-trapping agent price is 12000 yuan/ton, can calculate the urea-formaldehyde resin price that this preparation method prepares by above data and be approximately 1763 yuan/ton.And the glutinous agent price of commercially available environment protection type urea formaldehyde resin adhesive is greatly about 2500-2800 unit/ton.Be lower than the about 737-1037 of environment protection type urea formaldehyde resin price unit on the market on the urea-formaldehyde resin adhesive price of this preparation method preparation.Under the prerequisite that guarantees environmental protection, reduce cost again, had good market outlook.
Claims (4)
1. modified lignin resin is characterized in that: be that 40%-60% lignin derivative aqueous solution 120-160 part, aldehyde 20-60 part, lignin modification agent 5-30 part, xylogen activator 0.2-1.5 part are formed by mass percent concentration by weight;
Lignin derivative is one or more mixing by any ratio in sodium lignosulfonate, calcium lignin sulphonate, ammonium lignosulphonate, magnesium lignosulfonate, the alkali lignin;
Aldehyde be mass percent concentration be 35%-37% formaldehyde, 38%-40% acetaldehyde, 38%-40% oxalic dialdehyde, one or more mixing in the 50%-52% glutaraldehyde, 40%-42% propenal, 38%-40% furfural by any ratio;
The lignin modification agent is acrylamide, quadrol, trolamine, trimeric cyanamide, 1, and one or more in 4-butanediamine, thiocarbamide, the urea are by the mixing of any ratio;
The xylogen activator is one of 20%-25% aqueous sodium hydroxide solution, the 20%-25% trolamine aqueous solution, 20%-25% vulkacit H aqueous solution.
2. the preparation method of modified lignin resin according to claim 1 is characterized in that step is as follows:
Step 1: the massfraction of preparation 120-160 weight part is the lignin derivative aqueous solution of 40%-60%, adds 0.1-1 weight part xylogen activator, places the product that obtained step 1 in 1-48 hour;
Step 2: in the product of step 1, add the aldehyde of 20-60 weight part, at 50 ℃-85 ℃ reaction 30-120min, during keep the pH value of system to obtain the product of step 2 for 8.5-11;
Step 3: add the lignin modification agent of 5-30 weight part in the product of step 2, the xylogen activator that adds the 0.1-0.5 weight part reacted 1-5 hour under 50 ℃-85 ℃; Cooling, discharging.
3. an application rights requires the urea-formaldehyde resin of 1 described modified lignin resin, it is characterized in that: be made up of modified lignin resin 10-60 part, mass percent concentration 35%-37% formalin 160-208 part, 120 parts in urea, basic catalyst 0.02-0.05 part, an acidic catalyst 0.02-0.05 part, formaldehyde adsorbent 0.05-5 part by weight;
Basic catalyst is one of 20%-25% aqueous sodium hydroxide solution, the 20%-25% trolamine aqueous solution, the 20%-25% vulkacit H aqueous solution of mass percent concentration;
An acidic catalyst is one of 30%-35% aqueous formic acid, 30%-35% acetic acid aqueous solution, 5%-10% aqueous sulfuric acid, 20%-25% aqueous hydrochloric acid of mass percent concentration;
Formaldehyde adsorbent is one or more mixing by any ratio in trimeric cyanamide, acrylamide, polyvinyl alcohol, thiocarbamide, phenol, xylogen powder, tree bark powder, tannin, the starch.
4. the preparation method of urea-formaldehyde resin according to claim 3 is characterized in that step is as follows:
(1): the mass percent concentration 35%-37% formalin that in container, adds the 160-208 weight part, urea 60 weight parts, the formaldehyde in control addition stage and the mol ratio of urea are at 1.6-2.0, start whipping appts, regulate pH=9.0-9.3 with basic catalyst, be warming up to 85 ℃-95 ℃, insulation reaction half an hour;
(2): regulate pH=4.8-5.2 with an acidic catalyst, reaction 10min;
(3): add the urea of 20-40 weight part again, reaction 5min-20min. reacts to terminal, and adding basic catalyst adjusting pH value is 6.5-7.5;
(4): add the modified lignin resin of 10-60 weight part, under 85 ℃ of-95 ℃ of conditions, react 10-60min;
(5): be cooled to 60-80 ℃, add remaining 20-40 weight part urea and 0.05-5 parts by weight of formaldehyde sorbent material, reaction 10-40min;
(6): be cooled to below 40 ℃, regulate the pH value between 7.0-7.5, cooling discharging.
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|---|---|---|---|
| CN 201110118917 CN102241826B (en) | 2011-05-09 | 2011-05-09 | Modified lignin and urea-formaldehyde resin synthesized from same and preparation methods of modified lignin and urea-formaldehyde resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103044690A (en) * | 2012-12-19 | 2013-04-17 | 山东龙力生物科技股份有限公司 | Preparation method for high-activity enzymatic hydrolysis lignin |
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| CN103755974A (en) * | 2014-01-23 | 2014-04-30 | 单成敏 | Preparation method of lignin modified polyester polyol |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4177313A (en) * | 1978-11-28 | 1979-12-04 | Georgia-Pacific Corporation | Amine-modified lignosulfonate-extended phenol formaldehyde resins |
| CN1850933A (en) * | 2006-05-09 | 2006-10-25 | 山东泉林纸业有限责任公司 | Lignin Environmental-protection type adhesive and its preparing method |
-
2011
- 2011-05-09 CN CN 201110118917 patent/CN102241826B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4177313A (en) * | 1978-11-28 | 1979-12-04 | Georgia-Pacific Corporation | Amine-modified lignosulfonate-extended phenol formaldehyde resins |
| CN1850933A (en) * | 2006-05-09 | 2006-10-25 | 山东泉林纸业有限责任公司 | Lignin Environmental-protection type adhesive and its preparing method |
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