CN109666366B - Urea-formaldehyde resin waste material regenerated modified acrylate interpenetrating network structure polymer emulsion and preparation and curing method thereof - Google Patents
Urea-formaldehyde resin waste material regenerated modified acrylate interpenetrating network structure polymer emulsion and preparation and curing method thereof Download PDFInfo
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- CN109666366B CN109666366B CN201811559885.3A CN201811559885A CN109666366B CN 109666366 B CN109666366 B CN 109666366B CN 201811559885 A CN201811559885 A CN 201811559885A CN 109666366 B CN109666366 B CN 109666366B
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- urea
- formaldehyde resin
- emulsion
- network structure
- interpenetrating network
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- 229920000642 polymer Polymers 0.000 title claims abstract description 59
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- C—CHEMISTRY; METALLURGY
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C09D161/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C09D161/24—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with urea or thiourea
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
The invention relates to the technical field of coatings and coating, and discloses a urea-formaldehyde resin waste regenerated modified acrylate interpenetrating network structure polymer emulsion and a preparation and curing method thereof, wherein the polymer emulsion is prepared from the following raw materials in percentage by mass through an in-situ emulsion polymerization method: 0.1-10% of an emulsifier; 0.1-0.5% of an initiator; 0.01-0.4% of a pH regulator; 15-40% of vinyl monomer; 0.5-15% of functional monomer; 0-2% of a molecular weight regulator; 0-3% of cosolvent; 10-40% of regenerated urea-formaldehyde resin powder; the balance being water. The invention can efficiently recycle and utilize the urea-formaldehyde resin waste, changes waste into valuable, and the prepared urea-formaldehyde resin waste regenerated modified acrylate interpenetrating network structure polymer has various effects of solvent resistance, water resistance, alkali resistance, high toughness and high strength, has wide application and low price, and has extremely high market value and social value.
Description
Technical Field
The invention relates to the technical field of coatings and coating, in particular to a urea-formaldehyde resin waste regenerated and modified acrylate interpenetrating network structure polymer emulsion and a preparation and curing method thereof.
Background
Urea-formaldehyde resin (UF resin), is urea and formaldehyde polycondensed into initial urea-formaldehyde resin under the action of catalyst (alkaline or acid catalyst), then under the action of solidifying agent or adjuvant the insoluble and infusible thermosetting resin is formed. Urea-formaldehyde resin is generally water-soluble resin, and has the advantages of low price, sufficient raw materials and easy curing. The cured urea-formaldehyde resin is non-toxic, colorless, good in light resistance, hard and scratch-resistant, and the urea-formaldehyde resin contains polar oxygen atoms in the molecular structure, so that it has good adhesive force to object surface, and is the variety with the largest dosage in adhesive. Especially in the manufacture of various artificial boards in the wood processing industry, the urea-formaldehyde resin and the modified products thereof account for about 90 percent of the total dosage of the adhesive. However, UF resin has the defects of poor acid and alkali resistance, short storage time, high curing condition, brittle cured product without toughness and the like, and the application of the UF resin in other fields is severely limited. Even some urea-formaldehyde resin glues have a shelf life of even only 15 days.
The urea-formaldehyde resin waste is mainly solidified urea-formaldehyde resin waste, redundant materials and urea-formaldehyde resin polymer gelled in production and storage, the former is difficult to utilize in the prior art, and the latter is partially blended and utilized in new glue through chemical modification in the industry, but the bonding property is reduced, and the formaldehyde content is increased. The waste of the urea-formaldehyde resin contains formaldehyde, and the improper disposal of the waste can generate great social harm. Reducing the molar ratio of formaldehyde to urea becomes the main way to reduce the formaldehyde emission. The lower the F/U, the more easily an intermediate product having an active group is formed, the poorer the colloidal stability, and the more easily a gel phenomenon is formed.
The study on the regeneration of urea-formaldehyde resin gel was published in 2005 in "journal of chemical industry" volume 19, 8 by zhangyumin et al, university of Nanjing forestry, university college of Wood industry, and the regenerated resin of urea-formaldehyde resin gel was studied by selecting orthogonal L9(33) test, and the analysis test results gave the optimum process conditions of the regenerated resin of urea-formaldehyde resin gel: the mass ratio of formaldehyde (37%) to resin gel was 2.5: 1, the amount ratio of formaldehyde to urea final substances of the regenerated resin is 1.3: 1. the regenerated resin prepared under the condition is applied to press poplar multilayer boards, and the bonding strength meets the requirements of II-type boards.
As described in the above documents, it is common in industry to add a large amount of formaldehyde into gel for dissolution and dope the gel into new glue for recycling, but in this technique, the amount of formaldehyde dissolved in gel is large, which affects the environmental protection of glue, and after the gel is recycled into new glue, it has a certain negative effect on the adhesive property of new glue.
Chinese patent document ZL201310745020.7 discloses a method for toughening and modifying urea resin, which comprises the following steps: uniformly mixing a toughening agent acrylic polymer, a vinyl polymer or an acetal polymer with urea resin through dispersion equipment to obtain urea resin molding powder, wherein the toughening agent acrylic polymer, the vinyl polymer or the acetal polymer accounts for no more than 80% of the mass of the mixture; pressing 60-200 mesh urea-formaldehyde resin molding powder for 2-20 min at 80-200 ℃ and 5-60 MPa by using a flat vulcanizing machine to obtain an impact sample strip or a bending sample strip. The invention uses self-made toughener acrylic ester polymer or commercial acetal polymer or vinyl polymer to toughen and modify the urea-formaldehyde resin, wherein the best toughening effect is achieved by using the self-made acrylic ester polymer, the impact strength is 2.50kJ/m, and the bending strength is 85 MPa. The technology shows that the performance of the urea-formaldehyde resin modified by the acrylate polymer has a great improvement space, but the storage stability of the urea-formaldehyde resin is poor by using the method of doping the acrylate latex and the urea-formaldehyde resin, and the performance of the modified polymer is difficult to reach or exceed the stability, water resistance, alkali resistance, high toughness and the like of a pure acrylate polymer.
Interpenetrating Polymer Networks (IPNs) are interwoven Network polymers formed by interpenetration of two or more crosslinked polymers. The composite material is a new field of polymer blending modification technology development, and has the advantages of both physical blending and chemical copolymerization, so that the composite material has many valuable properties.
Depending on the method of synthesis, IPNs can be divided into different types, and they can be classified into synchronous IPNs (sin), stepwise IPNs (sipn), interpenetrating network elastomers (IEN), and latex IPNs (lipn). LIPN is an emerging IPN composite material. LIPN generally refers to a broad range of latex interpenetrating polymeric networks, and from a compositional standpoint, whether or not the polymers of such interpenetrating polymers are crosslinked, can be divided into two categories: LIPN and latex semi-IPN. The former means that both polymers forming the interpenetrating network are crosslinked, while the latter means that only one of the two polymers is crosslinked while the other is linear. IPN technology chemically performs molecular-level or supermolecular-level physical blending of multiple polymers, takes advantages of both physical blending and chemical copolymerization by using 'forced compatibility' and 'synergistic effect', and endows polymer materials with a plurality of valuable properties.
Disclosure of Invention
The invention firstly provides the urea-formaldehyde resin waste regenerated and modified acrylate interpenetrating network structure polymer emulsion, a coating film of the polymer emulsion is subjected to thermal crosslinking to form a high-molecular polymer film with an interpenetrating network structure, the polymer emulsion not only has the performance advantages of the urea-formaldehyde resin and the acrylate resin, but also obviously improves the overall water resistance, alkali resistance and other properties of the polymer.
The specific technical scheme is as follows:
the urea-formaldehyde resin waste material regenerated and modified acrylate interpenetrating network structure polymer emulsion is prepared from the following raw materials in percentage by mass through an in-situ emulsion polymerization method:
the balance being water.
Preferably, the cross-linked urea-formaldehyde resin modified acrylate interpenetrating network structure polymer emulsion is prepared from the following raw materials in percentage by mass through an in-situ emulsion polymerization method:
the balance being water.
When the formula of the optimized scheme is adopted, the coating film of the cross-linked urea-formaldehyde resin modified acrylic ester interpenetrating network structure polymer emulsion has better water resistance and alkali resistance.
The preparation method of the regenerated urea-formaldehyde resin powder comprises the following steps: physically crushing the cured urea-formaldehyde resin waste, redundant materials or urea-formaldehyde resin gel by using mechanical crushing equipment, wherein the particle size is larger than 35 meshes (less than 500 mu m) after crushing.
The emulsifier is a negative nonionic emulsifier and a reactive emulsifier containing reactivity.
The initiator is a free radical polymerization initiator; including oil soluble initiators and water soluble initiators.
The pH regulator is one or more of sodium pyrophosphate, sodium dihydrogen phosphate, sodium bicarbonate, ferrous sulfate and sodium chloride.
The vinyl monomer is one or more of Acrylic Acid (AA), methacrylic acid (MAA), Methyl Acrylate (MA), Methyl Methacrylate (MMA), Ethyl Acrylate (EA), ethyl methacrylate, Butyl Acrylate (BA), Butyl Methacrylate (BMA), cetyl acrylate, isooctyl acrylate (EHA), acrylonitrile, styrene (St), itaconic acid and vinyl acetate (VAc).
The functional monomer is one or more of N-methylol acrylamide (NMA), hydroxyethyl acrylamide (NHEMAA), diacetone acrylamide (DAAM), acetoacetoxy ethyl methacrylate (AAEMA), acetoacetoxyethyl methacrylate (AAEM), Glycidyl Methacrylate (GMA), hydroxyethyl methacrylate (HEMA), hydroxyethyl acrylate (HEA), hydroxypropyl acrylate (HPA), diallyl phthalate (DAP) and N- (N-butoxymethyl) acrylamide (IBMA).
The cosolvent is one or more of hexadecanol, hexadecane, hydrogenpolysiloxane (PHMS) n-hexanol, Isopropanol (IPA), polyvinyl alcohol (PVA), propylene glycol monomethyl ether acetate (PMA), propylene glycol butyl ether (PNB) and propylene glycol methyl ether (PM).
The molecular weight regulator is one or two of Mercaptoethanol (MCH), dodecyl mercaptan (NDM) and tert-dodecyl Mercaptan (MSDS).
The invention also provides a preparation method of the cross-linked urea-formaldehyde resin modified acrylate interpenetrating network structure polymer emulsion, which comprises the following steps:
(1) dissolving an oil-soluble initiator in a vinyl monomer, adding regenerated urea-formaldehyde resin powder according to the formula dosage, carrying out shearing dispersion, swelling and grinding in an ice bath, and then adding a functional monomer to obtain an oil phase part;
adding a part of the emulsifier with the formula amount into a part of the water with the formula amount to prepare emulsified water;
(2) adding the oil phase part into emulsified water, and shearing and emulsifying to prepare a pre-emulsion with the particle size of less than 1 mu m;
(3) adding the pH regulator and the emulsifier with the rest formula amount into the water with the rest formula amount to prepare a base solution;
(4) dropwise adding the pre-emulsion into the base solution, carrying out emulsion polymerization by adopting a starvation dropwise adding method, and heating to 45-90 ℃ for heat preservation after the pre-emulsion is completely dropwise added;
and then adding an initiator, preserving heat at 60-90 ℃, cooling, adding a salifying assistant and filtering to obtain a filtrate, namely the urea-formaldehyde resin waste regenerated modified acrylate interpenetrating network structure polymer emulsion.
Preferably, in the step (1), the time for shear dispersion is 0.5 to 1 hour.
Preferably, in the step (4), after the pre-emulsion is completely dripped, the temperature is raised to 45-90 ℃ for heat preservation for 0.5-1.5 hours; and after the initiator is added, keeping the temperature for 1-2 hours at 60-90 ℃.
In the step (4), the salifying assistant can regenerate modified acrylate interpenetrating network structure polymer emulsion with urea resin waste to form salt, and can be decomposed and volatilized during high-temperature curing, so that the acidity of the polymer is increased, and the curing and crosslinking of the polymer are facilitated.
Preferably, in the step (4), the salt-forming assistant is ammonia water or MP 95.
The preparation method of the invention adopts a high shear dispersion machine to shear and disperse the urea-formaldehyde resin swelled by vinyl monomer, and pre-emulsify under the action of pH regulator and emulsifier (reaction type emulsifier), uniformly disperse the urea-formaldehyde resin waste particles swelled by monomer in the emulsion particles of vinyl monomer in nanometer granularity, promote the mixture to initiate polymerization in the monomer droplets of pre-emulsion through an oil-soluble initiator dissolved in the monomer, form a stationary phase through the constraint action of the macromolecular network of the swelled urea-formaldehyde resin cross-linked polymer, and polymerize in the stationary phase, thereby forming the cross-linked urea-formaldehyde resin modified acrylate emulsion with interpenetrating network structure. The polymer can generate secondary crosslinking at high temperature after forming a film, so that a urea-formaldehyde resin system and an acrylate resin system respectively generate self-crosslinking reaction to generate a high-performance coating with an interpenetrating network structure.
The urea-formaldehyde resin network structure polymer can restrain the vinyl monomer swelled therein during polymerization, prevent phase separation and create conditions for preparing the urea-formaldehyde resin waste material regenerated modified acrylate interpenetrating network structure polymer. But in order to ensure the stability of the emulsion particles and prevent the precipitation of the urea-formaldehyde resin waste material caused by the nucleation of the micelles, the preparation method adopts a nucleation mechanism initiated in submicron monomer droplets, dissolves the oil-soluble initiator in the monomer, and swells the oil-soluble initiator in the urea-formaldehyde resin micro-and nano-particles together with the monomer for polymerization and molding.
The technique for initiating nucleation in submicron monomer droplets was first to suggest a new particle nucleation mechanism in Ugelstad et al, 1973. By introducing a small amount of emulsifier and co-emulsifier and combining with the fine emulsification dispersion technology, the monomer droplets form stable submicron particles (50-500nm), the specific surface area is greatly increased, and the free emulsifier forms micelles or stable homogeneous nucleation in the water phase. The monomer liquid drop becomes the main nucleation place in the polymerization process, which can effectively reduce the emulsion instability caused by diffusion and is easy to control the latex particle size and distribution.
The polymer emulsion prepared by the invention still has the water-resistant and alkali-resistant performances which reach or exceed those of pure acrylate emulsion when the content of the urea-formaldehyde resin is close to 50 percent. After being cured, the coating has the effects of water resistance, alkali resistance, transparency, high hardness and high toughness, and can be widely used in the fields of printing mucilage, coating, adhesive, coating paste and the like.
In the urea-formaldehyde resin waste regenerated and modified acrylate interpenetrating network structure polymer emulsion prepared by the method, urea-formaldehyde resin can be further crosslinked under an acidic condition, the acrylic emulsion is terminated by carboxyl and salified by ammonia water, and when the emulsion is cured to form a film, the carboxyl is exposed along with volatilization of the ammonia water, and the further crosslinking of the urea-formaldehyde resin is promoted by the increase of the acidity, so that the self-crosslinking of acrylate functional groups is accelerated. The residual peroxide in emulsion polymerization can promote the crosslinking of urea-formaldehyde resin, the crosslinking temperature of acrylic ester is different along with the crosslinking groups of functional monomers, such as DAAM, IBMA and the like which are normal-temperature crosslinking agents, but because the glass transition temperature of the polymer modified by urea-formaldehyde resin is higher, the film is difficult to form under the normal-temperature condition without the assistance of a film-forming assistant.
The invention also provides a curing method of the urea-formaldehyde resin waste regenerated modified acrylate interpenetrating network structure polymer emulsion, which comprises the following steps: and (3) spraying the urea-formaldehyde resin waste regenerated and modified acrylate interpenetrating network structure polymer emulsion to form a film, drying at 50-75 ℃, and then crosslinking and curing at 100-180 ℃.
Thus, the urea-formaldehyde resin and the acrylate polymer are respectively crosslinked under different conditions to form an interpenetrating network structure. The curing conditions can ensure the film forming conditions of the polymer film and also ensure the full crosslinking of the polymer.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention can efficiently recycle and utilize the solidified urea-formaldehyde resin waste, redundant materials and gel in the production and storage process of the urea-formaldehyde resin, obviously improve the utilization value of the waste and change waste into valuable, and create conditions for closed-cycle green development of the industry;
2. the polymer with the chain urea-formaldehyde resin reticular structure is combed through mechanical swelling, shearing and grinding modification, so that the polymer becomes urea-formaldehyde resin microspheres with moderate crosslinking degree, and the polymer is beneficial to in-situ polymerization of acrylic ester monomers which are bound to swell during polymerization and ensures the stability of the acrylic ester monomers in a polymerization process;
3. the invention uses the swelled urea-formaldehyde resin as A, and the monomer for swelling the resin is prepared into self-crosslinking vinyl polymer as B through a particle nucleation mechanism; the two polymers are doped with each other, and are crosslinked in different modes after being dried into a film, and finally the urea resin modified acrylate interpenetrating network structure polymer is formed;
4. the invention takes vinyl monomer as solvent, swells cross-linked urea-formaldehyde resin, and finally polymerizes the monomer, without solvent, and the process is advanced;
5. the invention perfects the technology of initiating nucleation in submicron monomer droplets by the effective matching of a polymerization process and a polymerization stabilizer, and prepares stable emulsion particles;
6. the urea resin modified acrylate interpenetrating network structure polymer prepared by the invention has the effects of solvent resistance, water resistance, alkali resistance, high toughness and high strength, is wide in application, low in price and has extremely high market value and social value.
Drawings
FIG. 1 is a transmission electron micrograph of the emulsion prepared in example 1, wherein (a) is a core-shell structure and (b) is a snowman structure;
FIG. 2 is a graph showing a particle size distribution of the emulsion obtained in example 1.
Detailed Description
The invention will be described in further detail below with reference to the drawings and examples, which are intended to facilitate the understanding of the invention without limiting it in any way.
1. The raw materials and sources in the following examples are shown in table 1:
TABLE 1 raw materials and sources
2. Preparation of regenerated urea-formaldehyde resin powder
After the urea resin waste is dried, a powder modified high-speed cooling mixing unit (50L of Macro machinery Co., Ltd., Zhang Home, Port) is used for preliminary stirring and crushing, so that the maximum particle size of the urea resin waste is less than 10mm, and then the urea resin waste is put into a high-speed crusher (multifunctional crusher, Asahi mechanical equipment Co., Ltd., Hangzhou) for crushing, wherein the particles of the solid waste are required to pass through a 120-mesh sieve. The coarser particles are further crushed and sieved. The screened particles are urea-formaldehyde resin powder. The gel-like urea-formaldehyde resin is only broken, and has no requirement on particle size.
Example 1
A method for regenerating cross-linked urea-formaldehyde resin and preparing a modified acrylate interpenetrating network structure polymer thereof comprises the following steps:
1. the formula (kilogram) is as follows:
a. pre-emulsion:
water phase:
oil phase:
b. base liquid beating:
c. replenishing an initiator:
10 parts of water;
0.2 part of APS.
2. Polymerization process
1) Dissolving an oil-soluble initiator AIBN in a BA monomer according to the formula amount of the pre-emulsion, adding other vinyl monomers, then swelling urea-formaldehyde resin powder in the vinyl monomers, carrying out shearing dispersion and grinding in a low-temperature cooling bath (ice bath) by using a high-shear homogenizing emulsifying machine for 60 minutes, shearing and dispersing urea-formaldehyde resin particles to be semitransparent or transparent, and adding a functional monomer to obtain vinyl monomer swelling and dispersion (oil phase part) of the urea-formaldehyde resin; simultaneously dissolving and dispersing other components in the pre-emulsion formula in water to form a water phase part;
2) slowly adding the water phase part into the oil phase part while stirring by using a high-shear homogenizing emulsifying machine for shearing and emulsifying, wherein the emulsifying time is 3-5 minutes, and preparing a pre-emulsion with the particle size of less than 1 mu m, wherein the emulsified pre-emulsion is required to be homogenized and stored for a long time without layering;
3) adding the primer solution into a 500-liter reaction kettle, dropwise adding the pre-emulsion into the reaction kettle, and carrying out emulsion polymerization by using a starvation reaction dropwise adding method, wherein the reaction temperature is 80 ℃, and the dropwise adding time is 3-3.5 hours. Heating to 85 ℃ after the emulsion is completely dripped, preserving heat for 1 hour, supplementing the initiator, preserving heat for 1.5 hours at 85 ℃ after supplementing the initiator, cooling to below 45 ℃, adding a proper amount of ammonia water, filtering by using 120-mesh filter cloth, discharging and packaging for later use. The emulsion appearance is shown in Table 2.
Example 2
A method for regenerating cross-linked urea-formaldehyde resin and preparing a modified acrylate interpenetrating network structure polymer thereof comprises the following steps:
1. the formula (kilogram) is as follows:
a. pre-emulsion:
water phase:
100 parts of water;
emulsifier NRS-105 parts;
emulsifier AE 321812 parts;
oil phase:
b. base liquid beating:
c. replenishing an initiator:
10 parts of water;
0.2 part of APS.
2. Polymerization process
1) Dissolving an oil-soluble initiator AIBN in a BA monomer according to the formula amount of the pre-emulsion, adding other vinyl monomers, then swelling urea-formaldehyde resin powder in the vinyl monomers, carrying out shearing dispersion and grinding in a low-temperature cooling bath (ice bath) by using a high-shear homogenizing emulsifying machine for 60 minutes, shearing and dispersing urea-formaldehyde resin particles to be semitransparent or transparent, and adding a functional monomer to obtain vinyl monomer swelling and dispersion (oil phase part) of the urea-formaldehyde resin; simultaneously dissolving and dispersing other components in the pre-emulsion formula in water to form a water phase part;
2) slowly adding the water phase part into the oil phase part while stirring by using a high-shear homogenizing emulsifying machine for shearing and emulsifying, wherein the emulsifying time is 3-5 minutes, and preparing a pre-emulsion with the particle size of less than 1 mu m, wherein the emulsified pre-emulsion is required to be homogenized and stored for a long time without layering;
3) and (2) adding the primer solution into a 500-liter reaction kettle, heating to 80 ℃ for reaction, continuing to react for 15 minutes after blue light appears, dropwise adding the pre-emulsion into the reaction kettle, and carrying out emulsion polymerization by using a starvation reaction dropwise adding method, wherein the reaction temperature is 80 ℃, and the dropwise adding time is 3-3.5 hours. Heating to 85 ℃ after the emulsion is completely dripped, preserving heat for 1 hour, supplementing the initiator, preserving heat for 1.5 hours at 85 ℃ after supplementing the initiator, cooling to below 45 ℃, adding a proper amount of ammonia water, filtering by using 120-mesh filter cloth, discharging and packaging for later use. The emulsion appearance is shown in Table 2.
Example 3
A method for regenerating cross-linked urea-formaldehyde resin and preparing a modified acrylate interpenetrating network structure polymer thereof comprises the following steps:
1. the formula (kilogram) is as follows:
a. pre-emulsion:
water phase:
oil phase:
b. base liquid beating:
c. replenishing an initiator:
10 parts of water;
KPS 0.2 parts;
0.08 part of sodium bisulfite.
2. Polymerization process
1) Dissolving an oil-soluble initiator BPO in a BA monomer according to the formula amount of a pre-emulsion, adding other vinyl monomers, then swelling urea-formaldehyde resin powder in the vinyl monomers, carrying out shearing dispersion and grinding in a low-temperature cooling bath (ice bath) by using a high-shear homogenizing emulsifying machine for 60 minutes, shearing and dispersing urea-formaldehyde resin particles to be semitransparent or transparent, and adding a functional monomer to obtain vinyl monomer swelling and dispersion (oil phase part) of the urea-formaldehyde resin; simultaneously dissolving and dispersing other components in the pre-emulsion formula in water to form a water phase part;
2) slowly adding the water phase part into the oil phase part while stirring by using a high-shear homogenizing emulsifying machine for shearing and emulsifying, wherein the emulsifying time is 3-5 minutes, and preparing a pre-emulsion with the particle size of less than 1 mu m, wherein the emulsified pre-emulsion is required to be homogenized and stored for a long time without layering;
3) the primer solution is added into a 500L reaction kettle, and nitrogen is introduced to expel oxygen. And (3) heating to 55 ℃, waiting for bottom-coating blue light to appear, dropwise adding the pre-emulsion into a reaction kettle after the blue light appears for 15 minutes, and carrying out emulsion polymerization by using a starvation reaction dropwise adding method, wherein the reaction temperature is 60 ℃, and the dropwise adding time is 3.5-4 hours. Heating to 70 ℃ after the emulsion is completely dripped, preserving heat for 1 hour, supplementing an initiator, preserving heat for 1.5 hours at 75 ℃ after supplementing the initiator, cooling to below 45 ℃, adding a proper amount of ammonia water, filtering by using 120-mesh filter cloth, discharging and packaging for later use. The emulsion appearance is shown in Table 2.
Example 4
A method for regenerating cross-linked urea-formaldehyde resin and preparing a modified acrylate interpenetrating network structure polymer thereof comprises the following steps:
1. the formula (kilogram) is as follows:
a. pre-emulsion:
water phase:
oil phase:
b. base liquid beating:
c. replenishing an initiator:
10 parts of water;
0.2 part of APS.
2. Polymerization process
1) Dissolving an oil-soluble initiator AIBN in a BA monomer according to the formula amount of the pre-emulsion, adding other vinyl monomers, then swelling urea-formaldehyde resin powder in the vinyl monomers, carrying out shearing dispersion and grinding in a low-temperature cooling bath (ice bath) by using a high-shear homogenizing emulsifying machine for 60 minutes, shearing and dispersing urea-formaldehyde resin particles to be semitransparent or transparent, and adding a functional monomer to obtain vinyl monomer swelling and dispersion (oil phase part) of the urea-formaldehyde resin; simultaneously dissolving and dispersing other components in the pre-emulsion formula in water to form a water phase part;
2) slowly adding the water phase part into the oil phase part while stirring by using a high-shear homogenizing emulsifying machine for shearing and emulsifying, wherein the emulsifying time is 3-5 minutes, and preparing a pre-emulsion with the particle size of less than 1 mu m, wherein the emulsified pre-emulsion is required to be homogenized and stored for a long time without layering;
3) adding the primer solution except the monomer into a 500-liter reaction kettle, heating to 90 ℃, adding the monomer, reacting for 30 minutes, cooling to 75 ℃, dropwise adding the pre-emulsion into the reaction kettle, and carrying out emulsion polymerization by using a starvation reaction dropwise adding method, wherein the reaction temperature is 75 ℃, and the dropwise adding time is 4-4.5 hours. Heating to 80 ℃ after the emulsion is completely dripped, preserving heat for 1 hour, supplementing an initiator, preserving heat for 1.5 hours at 85 ℃ after the initiator is supplemented, cooling to below 45 ℃, adding a proper amount of ammonia water, filtering by using 120-mesh filter cloth, discharging and packaging for later use. The emulsion appearance is shown in Table 2.
Example 5
The preparation process and preparation process of regenerated crosslinked urea-formaldehyde resin and modified acrylate interpenetrating polymer network structure polymer are as in example 1, with the only difference being that urea-formaldehyde resin powder in 50 weight portions and BA in 69 weight portions. The emulsion appearance is shown in Table 2.
Comparative example 1
A method for regenerating cross-linked urea-formaldehyde resin and preparing a modified acrylate interpenetrating network structure polymer thereof comprises the following steps:
1. the formula (kilogram) is as follows:
a. pre-emulsion:
water phase:
oil phase:
b. base liquid beating:
c. replenishing an initiator:
20 parts of water;
0.4 part of APS.
2. Polymerization process
1) According to the formula amount of the pre-emulsion, dissolving an oil-soluble initiator AIBN in a BA monomer, adding other monomers, and adding a functional monomer to obtain an oil phase part; simultaneously dissolving and dispersing other components in the pre-emulsion formula in water to form a water phase part;
2) slowly adding the water phase part into the oil phase part while stirring by using a high-shear homogenizing emulsifying machine for shearing and emulsifying, wherein the emulsifying time is 3-5 minutes, and preparing a pre-emulsion with the particle size of less than 1 mu m, wherein the emulsified pre-emulsion is required to be homogenized and stored for a long time without layering;
3) adding the primer solution into a 500-liter reaction kettle, dropwise adding the pre-emulsion into the reaction kettle, and carrying out emulsion polymerization by using a starvation reaction dropwise adding method, wherein the reaction temperature is 80 ℃, and the dropwise adding time is 3-3.5 hours. Heating to 85 ℃ after the emulsion is completely dripped, preserving heat for 1 hour, supplementing the initiator, preserving heat for 1.5 hours at 85 ℃ after supplementing the initiator, cooling to below 45 ℃, adding a proper amount of ammonia water, filtering by using 120-mesh filter cloth, discharging and packaging for later use. The emulsion appearance is shown in Table 2.
Comparative example 2
Half (230 kg) of the emulsion of comparative example 1 was taken, 50 kg of urea-formaldehyde resin powder was added, 116 kg of water was added, and a small amount of thickener was added to prepare a dope latex having a solid content close to that of comparative example 1 for future use. And thickens slightly to prevent precipitation of the filled urea-formaldehyde resin powder. The emulsion appearance is shown in Table 2.
Test example
1. Polymer coating Performance testing
Each of the examples and comparative examples was diluted one time with water and sprayed on a tin plate (film thickness after drying 45. + -.5 μm), and then dried at a constant temperature of 50 to 75 ℃ for 2 hours, followed by crosslinking and curing at 150 ℃ for 180 seconds. Finally, a water resistance test of the coating is carried out according to the GB/T1733-93 method, and the results are divided into the phenomena of constant, light loss, color change, bubbling, wrinkling, falling, rusting and the like; testing the adhesive force of a paint film according to GB/T9286-88, and grading according to a specified rating standard, wherein the grade 0 is the best, and the grade 5 is the worst; the hardness of the coated pencil was tested according to GB/T6739-86, using pencils ranging from 6B to 6H. The test results are shown in Table 2.
TABLE 2 appearance of polymer emulsion and its coating properties
| Source of emulsion | Appearance of the emulsion | Water resistance | Adhesion force | Hardness of paint film | |
| Example 1 | Milky white with blue light | Is not changed | 0 | 5H | |
| Example 2 | Milk white | Is not changed | 0 | 3H | |
| Example 3 | Milky white with blue light | Is not changed | 0 | 3H | |
| Example 4 | Milk white | Is not changed | 0 | 3H | |
| Example 5 | Milk white and good blue light | Is not changed | 0 | 3H | |
| Comparative example 1 | Translucent | Light loss | 0 | 2H | |
| Comparative example 2 | Milk | Color change | 2 | 2H |
2. The emulsion polymers obtained in the examples were subjected to a performance test
The emulsions prepared in the above examples were coated at 160g/m, respectively2The gluing amount on the glass fiber mesh cloth for enhancing the building strength is 13 to 15g/m2And drying conditions are as follows: 150 ℃ for 90 seconds. Testing the tensile breaking strength according to GB/T7689.5-2013; and testing the alkali-resistant retention rate according to GB/T20101-2006. The test results are shown in Table 3.
Table 3 results of performance testing of emulsion coated fiberglass mesh fabric products of examples
3. Transmission electron microscopy analysis
The emulsion obtained in example 1 was analyzed by transmission electron microscopy.
As shown in FIG. 1, the analysis was carried out using a 120kv Transmission Electron Microscope (TEM) instrument of Hitachi, Japan. Putting 1 drop of the emulsion into a conical flask, adding 50ml of phosphotungstic acid aqueous solution (the concentration is 1%) for dyeing, oscillating for five minutes under ultrasonic, standing for 40 minutes, dropping a little on a copper net, and observing the appearance under a transmission electron microscope after drying. The transmission electron microscope shows that most of the urea resin modified acrylic latex particles are regular spheres, have uniform sizes, are distributed between 150nm and 200nm in particle size, are ideal core-shell structures, and are partially snowman type atypical core-shell structures. In general, polymers of the LIPN structure have a core-shell structure.
4. Particle size analysis
The emulsion obtained in example 1 was subjected to particle size analysis.
As shown in FIG. 2, the emulsion was analyzed by Zetasizer Nano-ZS nanometer particle size Zeta potential Analyzer of Malvern, UK, and the average particle size was 252.2nm, the latex particles showed a monomodal distribution, and the particle size was consistent with the technique of nucleation of submicron monomer droplets-the particle size range of monomer droplets forming stable submicron particles (50-500 nm).
The above-mentioned embodiments are intended to illustrate the technical solutions and advantages of the present invention, and it should be understood that the above-mentioned embodiments are only specific embodiments of the present invention, and are not intended to limit the present invention, and any modifications, additions, equivalents, etc. made within the scope of the principles of the present invention should be included in the scope of the present invention.
Claims (6)
1. The urea-formaldehyde resin waste material regenerated and modified acrylate interpenetrating network structure polymer emulsion is characterized by being prepared from the following raw materials in percentage by mass through an in-situ emulsion polymerization method:
0.1-10% of an emulsifier;
0.1-0.5% of an initiator;
0.01-0.4% of a pH regulator;
15-40% of vinyl monomer;
0.5-15% of functional monomer;
0-2% of a molecular weight regulator;
0-3% of cosolvent;
10-40% of regenerated urea-formaldehyde resin powder;
the balance of water;
the preparation method of the regenerated urea-formaldehyde resin powder comprises the following steps: physically crushing the cured urea-formaldehyde resin waste, redundant materials or urea-formaldehyde resin gel, and crushing to obtain the particle size of more than 35 meshes or less than 500 mu m.
2. The urea-formaldehyde resin waste regeneration modified acrylate interpenetrating network structure polymer emulsion as claimed in claim 1, which is characterized in that the emulsion is prepared from the following raw materials by an in-situ emulsion polymerization method in percentage by mass:
0.1-3% of an emulsifier;
0.1-0.5% of an initiator;
0.01-0.4% of a pH regulator;
15-35% of vinyl monomer;
0.5-5% of functional monomer;
0-2% of a molecular weight regulator;
0-3% of cosolvent;
10-25% of regenerated urea-formaldehyde resin powder;
the balance being water.
3. The urea-formaldehyde resin waste regeneration modified acrylate interpenetrating network structure polymer emulsion as claimed in claim 1 or 2, wherein the vinyl monomer is one or more of acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, cetyl acrylate, isooctyl acrylate, acrylonitrile, styrene, itaconic acid and vinyl acetate.
4. The urea-formaldehyde resin waste regeneration modified acrylate interpenetrating network structure polymer emulsion as claimed in claim 1 or 2, wherein the functional monomer is one or more of N-methylol acrylamide, hydroxyethyl acrylamide, diacetone acrylamide, acetoacetoxyethyl methacrylate, glycidyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, diallyl phthalate and N- (N-butoxymethyl) acrylamide.
5. The urea-formaldehyde resin waste regeneration modified acrylate interpenetrating network structure polymer emulsion as claimed in claim 1 or 2, wherein the initiator is a radical polymerization initiator, and comprises an oil-soluble initiator and a water-soluble initiator.
6. The curing method of the urea-formaldehyde resin waste regenerated and modified acrylic ester interpenetrating network structure polymer emulsion as claimed in any one of claims 1 to 5, characterized by comprising the following steps: and (3) spraying the urea-formaldehyde resin waste regenerated and modified acrylate interpenetrating network structure polymer emulsion to form a film, drying at 50-75 ℃, and then crosslinking and curing at 100-180 ℃.
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Citations (3)
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| CN1215067A (en) * | 1997-10-20 | 1999-04-28 | 湖北大学 | Preparation of benzene propyl emulsion from waste polystrene foamed plastics |
| WO2002000429A1 (en) * | 2000-06-21 | 2002-01-03 | Agrolinz Melamin Gmbh | Fibre composites with excellent dimensional stability, weather resistance and flameproofing properties |
| CN108587395A (en) * | 2018-04-25 | 2018-09-28 | 武汉理工大学 | A kind of bilayer wave-absorbing coating material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1215067A (en) * | 1997-10-20 | 1999-04-28 | 湖北大学 | Preparation of benzene propyl emulsion from waste polystrene foamed plastics |
| WO2002000429A1 (en) * | 2000-06-21 | 2002-01-03 | Agrolinz Melamin Gmbh | Fibre composites with excellent dimensional stability, weather resistance and flameproofing properties |
| CN108587395A (en) * | 2018-04-25 | 2018-09-28 | 武汉理工大学 | A kind of bilayer wave-absorbing coating material and preparation method thereof |
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