Method of preparing alkali lignin modified phenolic resin
A, technical field The invention relates to a process for the preparation of the wood adhesive, especially relates to an environment-friendly alkali lignin modified phenolic resin preparation method. Second, the background technology Lignin is the only nature can provision of renewable resources non-aromatic-based compound. Lignin molecule contains aryl, phenolic hydroxyl group, an alcoholic hydroxyl, carbonyl, methoxy, carboxyl, conjugated double bond, and many other different types of chemical active functional group, and a renewable, biodegradable, non-toxic, and the like, industrial lignin derived from waste pulping and paper-making industry, low cost, excellent green, is thus to be regarded as environment-friendly chemical raw materials. Pulping and paper-making industry each year separated from plants 1.4 billion tons of cellulose, at the same time obtain 5000 million tons of lignin spinoffs, and as the evaporation concentration, the maturity of the spray drying technique, the annual output industrial lignin increasing year by year, but so far, produced by today's global each year in the industrial lignin less than 20% is effectively utilized. The phenolic resin in the performance of its excellent outdoor level is widely used in the production of plywood, adhesive strength is high, water-resistant, heat-resistant, corrosion-resistant, and the like are very good performance, but the phenol as petrochemical products and toxicity is relatively large, the use of renewable non-toxic lignin production of lignin phenolic resin in place of phenol, the consumption of the phenol can be reduced, and the waste, paper waste material to realize the purpose of resource management. Industrial lignin pulp paper-making process due to the different, is divided into a lignin sulfonate and alkali lignin. Lignin sulfonate contains the sulfonic group, the water-soluble, dispersible, better surface activity, in the preparation of lignin-based phenolic resin is the most environmentally friendly adhesive lignin sulfonate as raw materials, CN1632030 Patent includes in this regard, CN101104782, CN101260283. Because the lignin alkali insoluble under acidic conditions, color deep, poor performance, once deemed to be waste burned, waste of resources, polluting the environment. With the enhancement of environmental protection consciousness and the concern of the lack of petroleum resources, the alkali lignin gradually, through various modified means, substitute preparation environment-friendly adhesive petrescence resources. Preparing lignin lignin with a phenolic adhesive, mainly through blends the copolymerization process. CN101260283 has proposed a kind of the lignin phenol liquefied liquid-based process for the preparation of phenolic adhesive, after through lignin after phenol reaction with formaldehyde to make low free akdehyde environmental protective phenolic resin adhesive, than the traditional phenolic resin adhesive has a lower cost and lower free aldehyde content is, pressed into the plywood has good adhesion properties. However, the addition of too little lignin content, can not achieve the purpose of the utilization of waste material. The lignin alkaligenous the years of thousands of tons, but due to the lack of deep processing, the variety little lignin alkali, poor performance, its application range is limited, according to now also not a large-scale concrete application path. The invention relates to alkali lignin as raw materials, without extraction and purification processing, the copolymerization process of synthesizing the lignin phenol-formaldehyde resin, can replace 30-50% of the phenol, stable reaction is easy to control, easy industrialized production, the bonding strength for the level I, formaldehyde release reaches E0 level, is the development of environment-friendly biomass-based wood adhesive and the recycling of waste products provides a new way of utilizing. Three, the content of the invention Technical problem: the present invention provides a kind of alkali lignin phenolic resin preparation method of environmentally friendly adhesive, on the one hand can substitute part of the petroleum-based phenol raw material, reducing the cost, on the other hand, the source of the original can be fully utilized for the waste liquid from the papermaking, to achieve the purpose of the utilization of waste material. Technical proposal: alkali lignin modified phenolic resin preparation method, preparation steps are as follows: 1): phenol, formaldehyde solution 1st group, lignin alkali, metal oxide and dilution water added into the reactor, to rise to the 75-85 [...] , reaction 60-80min; formaldehyde and phenol on the molar amount of the ratio of 0.82 the [...] 1-1.04: 1 ; 2): to the reactor into the 2nd group of formaldehyde solution, the system in the 75-85 [...] to continue reaction 60-70min; accumulated by adding formaldehyde and phenol molar amount than for the 1.55 [...] 1-1.70: 1 ; 3): adding formaldehyde solution and 1st 3rd group batch alkali solution, the system in the 75-85 [...] to continue reaction 50-60min, cumulative added formaldehyde and phenol molar amount ratio is 2.20 the [...] 1-2.40: 1 ; 4): cooling to 70 the [...] , adding formaldehyde collecting agent and 2nd group of alkaline solution, 65-70 the reaction [...] 20-50min, cooling discharge; the adding amount of the lignin of the above-mentioned alkali for alternative 0.3-0.5 of the phenol, the adding amount of the metallic oxide to phenol of 0.2-0.5 wt %, the addition of the alkaline solution to phenol of the total amount of 30-40 wt % and 1st, the weight ratio of the second number is sequentially added to the 1 [...] 3.5, formaldehyde to phenol of the adding amount of the trapping agent 8-10wt %, dilution water in order to guarantee the adding quantity of the solid content of the whole system is controlled at 50 wt % in. The above-mentioned the lignin alkali sulphate process for making paper from paper mill waste is concentrated dried, wherein the active ingredient content of lignin ≥ 20 wt %. For the above-mentioned metal oxide is calcium oxide, zinc oxide or magnesium oxide. The above-mentioned alkaline solution as the quality for the concentration of 50% aqueous solution of NaOH, KOH aqueous solution, Ba (OH)2 aqueous solution or ammonia water. The above-mentioned collecting agent is urea formaldehyde. Beneficial effects: compared with the prior art, the invention has the following advantages: This invention adopts the copolymerization process for preparing alkali lignin phenolic resin adhesive, the phenol to the lignin, lignin and when generation of alkylphenol of methylation reaction, when small part of the alkylphenol with formaldehyde in the condensation polymerization reaction forming a backbone, most of the through the graft copolymer as the branched chain, thus introducing the lignin in the molecular chain, the purpose of the modified phenolic resin. Formaldehyde multi-batch gradually adding, the full reaction of formaldehyde and phenol, the free phenol content is reduced, and the appropriate amount of formaldehyde in the reaction the late addition of arsenic, make the residual formaldehyde quantity reduce, the free phenol obtained of low toxicity and low the aldehyde is even lignin phenolic glue. The invention is strictly controlled in the course of synthesizing pH value and degree of viscosity of the reaction, the method of feeding for several times, the reaction can be carried out rapidly in order, and the further low-temperature synthesis process for the promotion of the phenol, full reaction of formaldehyde, the synthetic resin of the free formaldehyde, free of the low. Preparation of phenolic resin of the free formaldehyde and free the phenol is even less than 0.25%. Lignin can replace 30-50% phenol, the bonding strength of the veneer preparing reach the state I of the required level. To join the woods 15-25% of flour, glue low cost, and pressing the synthetic resin used for the plywood placed 5-7 days of the formaldehyde i.e., less than 0.3 mg/L (drier method). Is an environment-friendly adhesive, to the development of environment-friendly biomass-based wood adhesive and the recycling of waste products provides a new way of utilizing. In the reaction of this invention the initial adding metal oxide, the metal oxide containing a monovalent or divalent metal ion, the increased proportion of ortho-the methylation of phenol, para-increase in freedom of uncured resin, the curing rate of the resin, reduce the temperature of hot plate. After the reaction medium by adding alkali, accompanied by the increase of pH value, advance the generated multi-dimensional hydroxymethyl phenol further polycondensation reaction with formaldehyde, desorbing a certain heat, add formaldehyde can offset the reduced temperature after the, is not needed in the production process of heating, the energy is saved. Lignin used in the invention is an alkali lignin, the waste liquid from the papermaking from papierfabrik sulphate process, the prepared concentrated after drying, raw materials are cheap, easy to obtain, sources are abundant, the waste liquid from the papermaking for papierfabrik sulfate method provides a new application route. Lignin alkali and used without extraction, purification processing, the concentrated black liquor directly to the powder as raw material after drying, will not cause the secondary pollution, reducing the pollution of the environment of black liquor, reach the utilization of waste material and the purpose of environmental protection, it has great economic significance and far-reaching social significance. In this invention of the phenolic resin of the lignin preparation process is simple, fast, and with good reproducibility, resin of good stability, long storage period, the cost is low. Four, specific embodiment The following embodiment is the mass concentration of alkali solution of 50% NaOH aqueous solution; on formaldehyde concentration: the present commercial formaldehyde solution in concentration 35-37% between, embodiment referred to the concentration of the solution of formaldehyde is 36.8%. Alternative 30-50wt % of the phenol: the adding amount of the lignin to the alkali / (phenol consumption amount of lignin alkali+)=0.3-0.5. Embodiment 1 1): in the 500 ml flask in four adding phenol to 100g, alkali lignin 44g, formaldehyde solution 1st group 80g, calcium oxide 0.2g, water 60g, the temperature is increased to 80 the [...] , reaction 80 min, 2): 2nd group of formaldehyde solution by 60g, 85 the reaction [...] 60 min. 3): 3rd number of formaldehyde solution by 60g, and adding alkali 1st group 10g, 85 the reaction [...] 60 min. 4): cooling to 70 the [...] , add urea 8g and 2nd group of lye 30g, 65 the reaction [...] 30 min, cooling discharge. Testing the performance of the, respectively, the results are listed in table 2. Pressing poplar plywood, to test their performance, the results are listed in table 3. Embodiment 2 1): in the 500 ml flask in four adding phenol to 100g, alkali lignin 44g, formaldehyde solution 1st group 75g, calcium oxide 0.5g, water 60g, to rise to the 75 [...] , reaction 70 min, 2): 2nd group of formaldehyde solution by 60g, 80 the reaction [...] 70 min. 3): 3rd number of formaldehyde solution by 60g, 1st group of alkali and 8g, 85 the reaction [...] 60 min. 4): cooling to 70 the [...] , add urea 8g and 2nd group of lye 30g, 65 the reaction [...] 20 min, cooling discharge. Testing the performance of the, respectively, the results are listed in table 2. Pressing poplar plywood, to test their performance, the results are listed in table 3. Embodiment 3 1): in the 500 ml flask in four adding phenol to 100g, alkali lignin 66g, formaldehyde solution 1st group 80g, calcium oxide 0.2g, water 90g, the temperature is increased to 80 the [...] , reaction 60 min, 2): 2nd group of formaldehyde solution by 60g, 85 the reaction [...] 70 min. 3): 3rd number of formaldehyde solution by 60g, and adding alkali 1st group 10g, 85 the reaction [...] 60 min. 4): cooling to 70 the [...] , add urea 8g and 2nd group of lye 30g, 70 the reaction [...] 30 min, cooling discharge. Testing the performance of the, respectively, the results are listed in table 2. Pressing poplar plywood, to test their performance, the results are listed in table 3. Embodiment 4 1): in the 500 ml flask in four adding phenol to 100g, alkali lignin 66g, formaldehyde solution 1st group 85g, calcium oxide 0.2g, water 90g, to rise to the 85 [...] , reaction 60 min, 2): 2nd group of formaldehyde solution by 60g, 85 the reaction [...] 70 min. 3): 3rd number of formaldehyde solution by 60g, and adding alkali 1st group 10g, 85 the reaction [...] 60 min. 4): cooling to 70 the [...] , add urea 10g and 2nd group of lye 28g, 65 the reaction [...] 50 min, cooling discharge. Testing the performance of the, respectively, the results are listed in table 2. Pressing poplar plywood, to test their performance, the results are listed in table 3. Embodiment 5 1): in the 500 ml flask in four adding phenol to 100g, alkali lignin 100g, formaldehyde solution 1st group 85g, calcium oxide 0.2g, water 130g, to rise to the 85 [...] , reaction 60 min, 2): 2nd group of formaldehyde solution by 60g, 85 the reaction [...] 70 min. 3): 3rd number of formaldehyde solution by 60g, 1st group of alkali and 7g, 85 the reaction [...] 60 min. 4): cooling to 70 the [...] , add urea 8g and 2nd group of lye 30g, 70 the reaction [...] 40 min, cooling discharge. Testing the performance of the, respectively, the results are listed in table 2. Pressing poplar plywood, to test their performance, the results are listed in table 3. Embodiment 6 1): in the 500 ml flask in four adding phenol to 100g, alkali lignin 100g, formaldehyde solution 1st group 90g, calcium oxide 0.2g, water 130g, to rise to the 75 [...] , reaction 60 min, 2): 2nd group of formaldehyde solution by 60g, 85 the reaction [...] 70 min. 3): 3rd number of formaldehyde solution by 60g, and adding alkali 1st group 10g, 85 the reaction [...] 60 min. 4): cooling to 70 the [...] , add urea 8g and 2nd group of lye 25g, 70 the reaction [...] 30 min, cooling discharge. Testing the performance of the, respectively, the results are listed in table 2. Pressing poplar plywood, to test their performance, the results are listed in table 3. Embodiment 7 The embodiment 1 in the step, the initial reaction is not adding metal oxide calcium oxide. Testing the performance of the, respectively, the results are listed in table 2. Pressing poplar plywood, to test their performance, the results are listed in table 3. Embodiment 8 Lignin is not added, to prepare phenolic resin: 1): in the 500 ml flask in four adding phenol to 100g, formaldehyde solution 1st group 72g, calcium oxide 0.2g, to rise to the 85 [...] , reaction 60 min, 2): 2nd group of formaldehyde solution by 60g, lye 1st group 10g, 85 the reaction [...] 50 min. 3): 3rd number of formaldehyde solution by 60g, 2nd group of alkali and 10g, 85 the reaction [...] 60 min. 4): cooling to 80 the [...] , add urea 10g and 2nd group of lye 25g, reaction 30 min, cooling discharge. Testing the performance of the, respectively, the results are listed in table 2. Pressing poplar plywood, to test their performance, the results are listed in table 3. Embodiment 9 1): in 2t reactor adding phenol to 400 kg, alkali lignin 250 kg, formaldehyde solution 1st group 32 kg, calcium oxide 1 kg, water 250 kg to rise to the 80 [...] , reaction 60 min, 2): 2nd group of formaldehyde solution to 240 kg, 80 °C reaction 70 min. 3): 3rd number of formaldehyde solution to 240 kg, 1st group of alkali and 50 kg, 80 °C reaction 60 min. 4): cooling to 70 the [...] , add urea 50 kg and 2nd group of alkali liquid 144 kg, 70 °C reaction 20 min, cooling discharge. Testing the performance of the, respectively, the results are listed in table 2. Pressing poplar plywood, to test their performance, the results are listed in table 3. Schedule 1: for the lignin component of alkali Ash contains a portion of the water insoluble substance, when the measuring sugar will also be brought into a portion of the water-insoluble material, in order to more intuitively-described composition, the water-insoluble substance are listed separately. Schedule 2 lignin technical indicators of phenolic resin Schedule 3 pressure plate test results Notes: schedule 4 in plywood strength is 14 sheet of the test piece detection results, the bonding strength is the average respectively, the denominator is the low intensity-the highest intensity. Add woods 15-25wt % of flour (to resin idea), the Gd 280-320g/m2 (double-sided) sizing, the jib closed 2-4h rear hot-pressing. Hot press temperature: the 135 ± 5 [...] ; pressure : 1.0 MPa; hot pressing time: 1 min/mm plate thickness. The detection of the above-mentioned resin: solid content according to GB/T14074-2006 the 3.5 require detection; viscosity according to GB/T14074-2006 the 3.3 require detection; free formaldehyde according to GB/T14074.16-93 detection; free phenol according to GB/T14074-2006 of 3.13 determination. Plywood detection: pressing of the veneer room temperature placed 5-7 days later detection. According to the bonding strength GB/T9846-2004 "plywood" method I types of plywood test, embodiment 1-7 rapid detection method according to the cooked in boiling water for 3h, the result measured is multiplied by the coefficient of 0.9; embodiment 8, 9 and by rapid detection method 100 the dashi [...] 4h, the 63 drying 20h, the 100 dashi [...] 4h detection; according to the formaldehyde emission from GB/T17657-1999 of in 4.12 detecting method for the dryer. A method for preparing alkali lignin modified phenol-formaldehyde resin comprises the following steps: phenol, a first batch of formaldehyde solution, alkali lignin, metal oxide and dilution water are added into a reactor; a second batch of formaldehyde solution is added into the reactor; and a third batch of formaldehyde solution and a first batch of alkaline solution are added, formaldehyde trapping agent and a second batch of alkaline solution are added, and then material is discharged after cooling. The invention adopts the copolymerization technique to prepare an alkali lignin phenol formaldehyde adhesive, lignin and the phenol are added simultaneously, obtained hydroxymethylated lignin is reacted with hydroxymethyl phenol, a small part of the obtained hydroxymethylated lignin participates in the polycondensation of the hydroxymethyl phenol to form a main chain, and a large part of the obtained hydroxymethylated lignin forms branch chains through graft copolymerization, therefore, the lignin is introduced into a molecular chain and the aim of modifying phenol-formaldehyde resin is achieved. The invention can replace the use of 30-50 percent of the phenol, realizes stable and easy reaction control and easy industrial production; the bonding strength satisfies the requirements of national I-level plates; formaldehyde release reaches E0 level; therefore, the invention provides a new approach to the development of environment-friendly biomass-based wood adhesive and resource utilization of waste materials. 1. Alkali lignin modified phenolic resin preparation method, is characterized in that the preparation steps are as follows: 1): phenol, formaldehyde solution 1st group, lignin alkali, metal oxide and dilution water added into the reactor, to rise to the 75-85 [...] , reaction 60-80min; formaldehyde and phenol on the molar amount of the ratio of 0.82 the [...] 1-1.04: 1; 2): to the reactor into the 2nd group of formaldehyde solution, the system in the 75-85 [...] to continue reaction 60-70 min; accumulated by adding formaldehyde and phenol molar amount than for the 1.55 [...] 1-1.70: 1; 3): adding formaldehyde solution and 1st 3rd group batch alkali solution, the system in the 75-85 [...] to continue reaction 50-60min, cumulative added formaldehyde and phenol molar amount ratio is 2.20 the [...] 1-2.40: 1; 4): cooling to 70 the [...] , adding formaldehyde collecting agent and 2nd group of alkaline solution, 65-70 the reaction [...] 20-50min, cooling discharge; The adding amount of the lignin of the above-mentioned alkali for alternative 30-50% of the phenol, the adding amount of the metallic oxide to phenol of 0.2-0.5 wt %, the addition of the alkaline solution to phenol of the total amount of 30-40 wt % and 1st, the weight ratio of the second number is sequentially added to the 1 [...] 3.5, formaldehyde to phenol of the adding amount of the trapping agent 8-10wt %, dilution water in order to guarantee the adding quantity of the solid content of the whole system is controlled at 50 wt % in. 2. Alkali lignin modified phenolic resin preparation method according to Claim 1, characterized in that the lignin alkali sulphate process for making paper from paper mill waste is concentrated dried, wherein the active ingredient content of lignin ≥ 20 wt %. 3. Alkali lignin modified phenolic resin preparation method according to Claim 1, is characterized in that the metal oxide is calcium oxide, zinc oxide or magnesium oxide. 4. Alkali lignin modified phenolic resin preparation method according to Claim 1, characterized in that the alkaline solution used for concentration of 50% aqueous solution of NaOH, KOH aqueous solution, Ba (OH)2 aqueous solution or ammonia water. 5. Alkali lignin modified phenolic resin preparation method according to Claim 1, is characterized in that the formaldehyde to a urea trap. Wt % content of 3.4 37.38 20.12 35.36 3.74 3.51 Embodiment 1 0.21 0.24 196 48.4 > 20 Embodiment 2 0.23 0.25 210 49.2 > 20 Embodiment 3 0.18 0.23 285 48.5 > 20 Embodiment 4 0.20 0.18 265 48.1 > 20 Embodiment 5 0.19 0.20 425 49.2 > 20 Embodiment 6 0.22 0.21 468 48.9 > 20 Embodiment 7 0.17 0.22 350 48.2 > 20 Embodiment 8 0.11 0.08 225 49.4 > 20 Embodiment 9 0.23 0.16 178 48.9 > 20