High-performance water-based acrylic ester floor latex emulsion, preparation method and application thereof

Abstract

The application discloses a high-performance water-based acrylate floor latex emulsion and a preparation method and application thereof. The emulsion is prepared from raw materials containing the following components in parts by weight: 150-250 parts of soft monomers, 150-200 parts of hard monomers, 5-15 parts of functional monomers, 1-5 parts of crosslinking monomers, 10-40 parts of cyclic alkenyl ketone monomers, 6-11 parts of emulsifiers, 5-7 parts of pH buffers, 7-15 parts of initiators and 0.1-1.0 parts of catalysts. The water-based emulsion provided by the application has excellent bonding performance, strong peeling force, no drumming and no edge lifting after lamination, and can meet the demand of high-end floor glue paving industry.

Description

TECHNICAL FIELD

[0001] The present application relates to an acrylate emulsion, in particular to a high-performance water-based acrylate floor emulsion and its preparation method and application. BACKGROUND

[0002] The mainstream floor glue on the market generally uses acrylate copolymer emulsion. When used, the glue is coated on the cement surface by a scraper, and after 20-30 minutes of natural environment, the glue is dehydrated to form a film. Then the PVC floor is attached to the cement surface, and after pressing under a certain pressure, the floor glue and the cement surface are bonded. Therefore, the floor glue has a wide application in the field of building floor paving.

[0003] With the increasing demand for safe and environmentally friendly decorative materials, the development of water-based acrylate floor emulsion has become increasingly important. However, most existing water-based acrylate emulsions have weak bonding strength, leading to problems such as PVC floor drumming and edge lifting. The development of high-performance water-based environmentally friendly water-based acrylate floor emulsion is of great significance to meet the needs of the high-end floor glue paving industry.

[0004] Chinese patent CN113845870A prepared a water-based floor glue by adding a pyrolysis latent curing agent with high price, and combined with the use of heat pressing operation in actual floor laying operation, which reduces the construction efficiency and has high cost in actual application, and is difficult to scale up. Chinese patent CN111892889A discloses a floor adhesive based on water-based acrylate resin and its preparation process. When used, the floor adhesive and isocyanate curing agent need to be mixed. In the actual construction process, the floor adhesive needs to be prepared first and then used, which increases the construction difficulty and the prepared finished floor adhesive needs to be used up in a short time, otherwise the finished adhesive has the risk of curing into waste, which is difficult to scale up. SUMMARY

[0005] To solve the above technical problems, the present application provides a high-performance water-based acrylate floor emulsion and its preparation method and application. The water-based emulsion provided by the present application has excellent bonding performance and strong peeling force, and will not drum or lift after being attached, which can meet the needs of the high-end floor glue paving industry.

[0006] To achieve the above purpose, the technical scheme adopted by the present application is as follows:

[0007] A high-performance water-based acrylate floor emulsion is prepared from raw materials containing the following weight parts:

[0008] soft monomer 150-250 parts, preferably 170-230 parts,

[0009] hard monomer 150-200 parts, preferably 165-190 parts,

[0010] functional monomer 5-15 parts, preferably 7-13 parts,

[0011] crosslinking monomer 1-5 parts, preferably 1.5-4.0 parts,

[0012] cycloalkenone monomer 10-40 parts, preferably 15-35 parts,

[0013] emulsifier 6-11 parts, preferably 7-10 parts,

[0014] pH buffer 5-7 parts, preferably 5.5-6.5 parts,

[0015] initiator 7-15 parts, preferably 8-13 parts,

[0016] catalyst 0.1-1.0 parts, preferably 0.2-0.7 parts.

[0017] In preferred embodiments of the application, the soft monomer is one or more of isooctyl acrylate, n-butyl acrylate, ethyl acrylate, lauryl acrylate, lauryl methacrylate;

[0018] Preferably, the hard monomer is one or more of methyl methacrylate, ethyl methacrylate, methyl acrylate, vinyl acetate, styrene, acrylonitrile;

[0019] Preferably, the functional monomer is an unsaturated monomer containing a carboxyl or hydroxyl group, preferably one or more of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate;

[0020] Preferably, the crosslinking monomer is one or more of acetoacetoxyethyl methacrylate, diacetone acrylamide, adipic dihydrazide, acrylamide.

[0021] In preferred embodiments of the application, the cycloalkenone monomer is one or more of 2-cyclopentenone, 2-cyclohexenone, 2-cycloheptenone.

[0022] In preferred embodiments of the application, the emulsifier is one or more of polyaryl sulfo succinic acid polyether ester salt, sodium dodecyl diphenyl ether disulfonate, polyphenyl styrene based rosin acid polyoxyethylene ether sulfate ammonium salt, polyaryl polyether phosphate sodium salt;

[0023] Preferably, the pH buffer is sodium carbonate and / or ammonium bicarbonate;

[0024] Preferably, the initiator is azobisisobutyronitrile and / or potassium persulfate;

[0025] Preferably, the catalyst is one or more of FeCl3·6H2O, CO(NO3)2·6H2O, Ni(NO3)2·6H2O.

[0026] In a preferred embodiment of the present application, the floor latex emulsion is prepared by emulsion polymerization.

[0027] A method for preparing a high-performance water-based acrylate floor latex emulsion as described herein, characterized in that it comprises the following steps:

[0028] 1) Add emulsifier, water, pH buffer and catalyst to the reaction kettle, heat to 70-80°C and start stirring;

[0029] 2) Prepare mixed monomers: mix all soft monomers, hard monomers, functional monomers, crosslinking monomers and cycloalkenone monomers uniformly to obtain mixed monomers;

[0030] 3) Add mixed monomers and 60-80% of the total amount of initiator solution to the reaction kettle under stirring conditions, and start polymerization; the polymerization reaction temperature is 80-85°C, and the reaction time is 1.5-2h;

[0031] 4) Continue to add the remaining initiator solution at the same reaction temperature, and continue to react for 1.5-2h;

[0032] 5) After holding for 0.5-1.0h, cool to 25-35°C, then adjust the pH to neutral, and filter the product.

[0033] In a preferred embodiment of the present application, the solid content of the emulsion is 40-55%.

[0034] Preferably, the glass transition temperature of the emulsion copolymer is -50°C to -20°C.

[0035] A high-performance water-based acrylate floor latex emulsion as described herein and a high-performance water-based acrylate floor latex emulsion prepared by the method described herein for use in floor glue.

[0036] In a preferred embodiment of the present application, the floor latex emulsion is blended with optional wetting agent, defoamer and thickening agent to prepare floor glue;

[0037] Preferably, the wetting agent is selected from one or more of Solvay OT-75, BASF WE3485, BYK-346;

[0038] Preferably, the defoamer is selected from one or more of Solvay DF-691, BASF 2410, HENKEL 7072;

[0039] Preferably, the thickening agent is selected from one or more of ammonia, AMP95, Wanhua A801, Wanhua A401, Wanhua U604.

[0040] In a preferred embodiment of the present application, the amount of the wetting agent added is 0.3-1.0% of the mass of the floor adhesive emulsion;

[0041] Preferably, the amount of the defoaming agent added is 0.1-1.0% of the mass of the floor adhesive emulsion;

[0042] Preferably, the amount of the thickening agent used is such that the viscosity of the floor adhesive is 30,000-50,000 cps.

[0043] The present application uses cyclic alkenyl ketone as a modified component of the floor adhesive emulsion, and unexpectedly finds that the obtained floor adhesive has improved bonding and peeling strength, and the post-peeling force is also improved, which can avoid problems such as floor drumming and edge lifting, and it is speculated that the possible mechanism of action is that the cyclic alkenyl ketone monomer participates in the copolymerization reaction together, thereby introducing a high-rigidity ring into the chain segment structure of the copolymer, so that the cohesion of the finished product is significantly improved. DETAILED DESCRIPTION

[0044] The present application will be further described below through specific examples, and the examples described in the present application are only used to illustrate the present application and do not limit the scope of the present application.

[0045] In the following examples of the present application, the main raw material information is shown in Table 1, and other raw materials and reagents are commercially available unless otherwise specified.

[0046] Table 1, main raw material information

[0047]

[0048]

[0049] The main test methods used in the present application are as follows:

[0050] 1. Initial peeling force: use an A2 spatula to evenly apply the floor adhesive to a standard cement board, and place it in a 23±2℃, 50±5% RH environment for 30 minutes. Cut a 25mm wide, 150mm long PVC substrate and attach it to the adhesive surface, and slowly press it four times using a 2kg standard roller. Place the prepared sample in a constant temperature and humidity chamber for 24 hours, and test the 180° peeling force according to the FINAT FTM-1 standard.

[0051] 2. Post-peeling force: according to the method in the initial peeling force test, prepare a sample with a PVC substrate attached to the surface, and place it in a 23±2℃, 50±5% RH environment for 4 days, and test the 180° peeling force according to the FINAT FTM-1 standard.

[0052] 3. Viscosity: Viscosity test was performed using Brookfield, LV viscometer at 64# / 12 rpm, 25℃.

[0053] 4. pH value: According to GB / T 14518-1993.

[0054] 5. Loop tack: The floor adhesive was evenly coated on a 100 μm thick PET film using a 50 μm wire bar, dried in a 100℃ oven for 2 min, and a layer of release paper was placed on the adhesive surface. The sample was placed in a 23±2℃, 50±5% RH environment for 24 h, and tested according to FINAT FTM-9.

[0055] Example 1

[0056] The water-based acrylate floor adhesive emulsion was prepared according to the following method:

[0057] 1) 5 g PS110, 4 g BSM-108, 5.5 g ammonium bicarbonate, 0.2 g FeCl3·6H2O, and 200 g deionized water were added to the reaction kettle, heated to 78℃ and the stirring was started, the temperature rising time was 15 min; the stirring speed was 260 r / min;

[0058] 2) 180 g 2-EHA, 30 g BA, 60 g MA, 100 g St, AN 10 g, 10 g AA, 3.8 g AAEM, and 30 g 2-cyclopentenone were mixed uniformly to obtain a mixed monomer; the mixing and stirring time of the above monomers was 30 min, and the mixing and stirring speed was 240 r / min;

[0059] 3) 11.5 g KSP was mixed with 190 g deionized water to obtain 201.5 g initiator solution;

[0060] 4) The mixed monomer and 75% of the initiator solution based on the total mass of the initiator solution were simultaneously added dropwise to the reaction kettle, and the polymerization was initiated under stirring, the polymerization reaction temperature was 85℃, the reaction time was 1.5 h; the stirring speed was 250 r / min;

[0061] 5) The remaining initiator solution was added dropwise, and the dropwise addition time was 1.5 h;

[0062] 6) After the end, the temperature was kept for 1 h; the temperature was lowered to 35℃, the emulsion pH was adjusted to about 7.0 by 10 wt% sodium hydroxide solution, filtered through a 100 mesh filter screen, and discharged.

[0063] The water-based acrylate floor adhesive emulsion prepared in this example had a solid content of 53.3%, and the glass transition temperature of the copolymer was -20℃.

[0064] Example 2-10

[0065] Different water-based acrylic floor glue emulsions were prepared according to the method in Example 1, with the only difference being that the raw material selection and dosage were adjusted according to the information in Table 2.

[0066] Table 2, raw material selection and dosage (g) in each example

[0067]

[0068]

[0069]

[0070] Comparative Example 1

[0071] A water-based acrylic floor glue emulsion was prepared according to a method substantially the same as Example 1, with the only difference being that 2-cyclopentenone was not added.

[0072] Comparative Example 2

[0073] A water-based acrylic floor glue emulsion was prepared according to a method substantially the same as Example 1, with the only difference being that FeCl3·6H2O was not added.

[0074] Comparative Example 3

[0075] A water-based acrylic floor glue emulsion was prepared according to a method substantially the same as Example 7, with the only difference being that the amount of 2-cyclopentenone added was modified to 50 g.

[0076] The water-based acrylic floor glue emulsions prepared in each example and comparative example were respectively tested for solid content and glass transition temperature (Tg), and the results are shown in Table 3.

[0077] Table 3, performance test of water-based acrylic floor glue emulsion

[0078]

[0079]

[0080] In addition, water-based acrylic floor glue emulsions prepared in each example and comparative example were respectively used as raw materials, WE3485 wetting agent (0.5% of the emulsion mass) and DF691 defoaming agent (0.5% of the emulsion mass) were added, and 10% ammonia water was added to stir and adjust the viscosity to prepare floor glue, and the annular initial adhesion, initial peeling force and late peeling force were tested, and the test results are shown in Table 4.

[0081] Table 4, performance test results of floor glue

[0082]

[0083]

[0084] Note: In the later stage of the test, the peel strength of examples 1-10, until the PVC substrate is torn, also did not peel off the standard cement board, indicating that the post-peeling strength of the floor glue is greater than the strength of the substrate, and the bonding performance is excellent.

[0085] The floor glue emulsion provided by the present application not only contains only water-based components which are safe and environmentally friendly, but also, as can be seen from the above test results, the floor glue prepared from the emulsion provided by examples 1-10 has very obviously improved the bonding and strength of the sample compared with comparative example 1, especially the post-peeling force of the test can reach the effect of material breaking, the glue layer strength is greater than the PVC substrate strength, and it can fully meet the use requirements of downstream customers.

[0086] The above is only the preferred embodiment of the present application, it should be pointed out that for ordinary skilled in the art, without departing from the method of the present application, a number of improvements and supplements can also be made, these improvements and supplements should also be considered as the protection scope of the present application.

Claims

1. A high performance waterborne acrylate floor latex emulsion characterized in that, Prepared from raw materials comprising the following weight parts: Soft monomer 150-250 parts, Hard monomer 150-200 parts, Functional monomer 5-15 parts, Crosslinking monomer 1-5 parts, Cycloalkenone monomer 10-40 parts, Emulsifier 6-11 parts, pH buffer 5-7 parts, Initiator 7-15 parts, Catalyst 0.1-1.0 parts; The catalyst is FeCl3·6H2O.

2. The high performance waterborne acrylate floor latex emulsion according to claim 1, characterized in that, Prepared from raw materials comprising the following weight parts: Soft monomer 170-230 parts, Hard monomer 165-190 parts, Functional monomer 7-13 parts, Crosslinking monomer 1.5-4.0 parts, Cycloalkenone monomer 15-35 parts, Emulsifier 7-10 parts, pH buffer 5.5-6.5 parts, Initiator 8-13 parts, Catalyst 0.2-0.7 parts.

3. The high performance waterborne acrylate floor latex emulsion according to claim 1, characterized in that, The soft monomer is one or more of isooctyl acrylate, n-butyl acrylate, ethyl acrylate, lauryl acrylate, lauryl methacrylate.

4. The high performance waterborne acrylate floor latex emulsion according to claim 3, characterized in that, The hard monomer is one or more of methyl methacrylate, ethyl methacrylate, vinyl acetate, styrene, acrylonitrile.

5. The high performance waterborne acrylate floor latex emulsion according to claim 3, characterized in that, The functional monomer is an unsaturated monomer containing carboxyl or hydroxyl groups.

6. The high performance waterborne acrylate floor latex emulsion according to claim 5, characterized in that, The functional monomer is one or more of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate.

7. The high performance waterborne acrylate floor latex emulsion according to claim 3, characterized in that, The crosslinking monomer is one or more of acetoacetoxyethyl methacrylate, diacetone acrylamide, adipic dihydrazide, acrylamide.

8. The high performance waterborne acrylate floor latex emulsion according to claim 1, characterized in that, The cycloalkenone monomer is one or more of 2-cyclopentenone, 2-cyclohexenone, 2-cycloheptenone.

9. The high performance waterborne acrylate floor latex emulsion according to any one of claims 1-8, characterized in that, The emulsifier is one or more of polyaryl sulfonic polyether ester salt, sodium dodecyl diphenyl ether disulfonate, polyphenyl styrene-based rosin acid polyoxyethylene ether sulfate ammonium salt, polyaryl polyether phosphate sodium salt.

10. The high performance waterborne acrylate floor latex emulsion according to claim 9, characterized in that, The pH buffer is sodium carbonate and / or ammonium bicarbonate.

11. The high performance waterborne acrylate floor latex emulsion according to claim 9, characterized in that, The initiator is azobisisobutyronitrile and / or potassium persulfate.

12. The high performance waterborne acrylate floor latex emulsion according to any one of claims 1-8, characterized in that, The floor latex emulsion is prepared by emulsion polymerization.

13. A process for the preparation of a high performance waterborne acrylate floor latex emulsion as claimed in any one of claims 1 to 12, characterized in that, Comprising the following steps: 1) Add emulsifier, water, pH buffer and catalyst to the reaction kettle, heat to 70-80℃ and start stirring; 2) Prepare mixed monomers: mix all soft monomers, hard monomers, functional monomers, crosslinking monomers and cycloalkenone monomers uniformly to obtain mixed monomers; 3) Add mixed monomers and 60-80% of the total amount of initiator solution to the reaction kettle under stirring conditions, and start polymerization; the polymerization reaction temperature is 80-85℃, and the reaction time is 1.5-2h; 4) Without changing the reaction temperature, add the remaining initiator solution and continue to react for 1.5-2h; 5) After holding for 0.5-1.0h, cool to 25-35℃, then adjust the pH to neutral, and filter the product.

14. The method for preparing the high-performance waterborne acrylic flooring latex according to claim 13, characterized in that, The solid content of the emulsion is 40-55%.

15. The method for preparing the high-performance water-based acrylic flooring latex according to claim 14, characterized in that, The glass transition temperature of the emulsion copolymer is -50℃ to -20℃.

16. Use of the high-performance water-based acrylate floor glue emulsion of any one of claims 1-12 or the high-performance water-based acrylate floor glue emulsion prepared by the method of any one of claims 13-15 in floor glue.

17. Use according to claim 16, characterized in that, The floor glue emulsion is blended with optional wetting agent, defoaming agent and thickening agent to prepare floor glue.

18. The use according to claim 17, characterized in that, The wetting agent is selected from one or more of Solvay OT-75, BASF WE3485, BYK-346.

19. The use according to claim 17, characterized in that, The defoaming agent is selected from one or more of Solvay DF-691, BASF 2410, HENKEL 7072.

20. The use according to claim 17, characterized in that, The thickening agent is selected from one or more of ammonia, AMP95, Wanhua A801, Wanhua A401, Wanhua U604.

21. Use according to any one of claims 17 to 20, characterized in that, The wetting agent is added in an amount of 0.3-1.0% of the mass of the floor glue emulsion.

22. The use according to claim 21, characterized in that, The defoaming agent is added in an amount of 0.1-1.0% of the mass of the floor glue emulsion.

23. The use according to claim 21, characterized in that, The thickening agent is used in an amount to make the viscosity of the floor glue 30000-50000 cps.

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